Oligosaccharide analogues of polysaccharides: Part 15: Oligomers of cellobiose-derived dialkynes and first crystal structure of an anomeric pair of trichloroacetimidates

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Oligosaccharide Analogues of Polysaccharides

Part 15

Oligomers of Cellobiose-Derived Dialkynes and First Crystal Structure of an

Anomeric Pair of Trichloroacetimidates¹)

by Alexander Ernst, W. Bernd Schweizer, and Andrea Vasella*

Laboratorium für Organische Chemie, ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich

Dedicated to the Memory of Steffen Vorwerk

The cellobiose-derived dimer 18, tetramer 48, and octamer 49 have been prepared. Acetolytic

debenzylation transformed the dimer 15, obtained from the partially benzylated, dialkynylated cellobiose 2

(Scheme 1), into 16 that was deacetylated to 18 (Scheme 2), but the analogous debenzylation of the tetramer 14

proved unsatisfactory. We, therefore, avoided benzyl groups and prepared the cellobiose-derived monomer 32

by glycosidation of 27 with the crystalline trichloroacetimidates 30 or 31 (Scheme 3). The acceptor 27 was

synthesised from 1,6-anhydroglucose in 7 steps (48% overall yield), and the trichloroacetimidates 30 and 31

were obtained in good overall yields from the alkynylated glucopyranoses 29 (Scheme 3). The structure of the

anomeric trichloroacetimidates 30 and 31 was determined by single crystal X-ray analysis. The alkyne 34,

orthogonally C-protected by SiMe₃and GeMe₃groups, was transformed by a binomial strategy into the dimer

37, the tetramer 41, and the octamer 47 (Scheme 4). The unprotected mono- and oligomers 1, 18, 48, and 49 are

soluble in H₂O, MeOH, and DMSO. Their ¹H-NMR specta ((D₆)DMSO (1, 18, 48, 49), CD₃OD (1, 18, 48), D₂O

(49)) show no signs of association.

Introduction. ± We plan to assess the influence of H-bonds on the structure and

properties of cellulose by comparing cellooligosaccharides with a series of ꢀacetyleno-

oligosaccharidesꢁ obtained from glucose- and cellobiose-glycans, and from higher b-d-

1,4-glycans. In these, all or some glycosidic O-atoms are replaced by a butadiynediyl

unit [1]. We have prepared a series of glucose-derived oligomers (up to the octamer),

where no intramolecular H-bonds between the pyranose residues are possible [2][3].

We have also prepared the cellobiose-derived dialkyne 1 (Fig. 1) [4], which still possesses

the strong intramolecular C(5) OH ´´´ O C(5') H-bond typical for cellobiose [5][6].

Analogues of the glucose- and the cellobiose-derived series thus possess either none

or one intramolecular H-bond in the monomeric unit, and this difference is expected to

Fig. 1. Structure of the deprotected monomer 1 (adapted

from [4]). The dotted line indicates the C(5') O ´´´

HO C(5) intramolecular H-bond.

1

)

Presented in part at the Royal Society of Chemistry Carbohydrate Group Spring Meeting, Birmingham,

1998, Abstract No. 9.

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strongly affect the structure and properties of the analogues. Force-field calculations

predict that the ꢀacetyleno-oligosaccharidesꢁ of the glucose-derived series possess a

more or less linear, rigid-rod like shape [7]. Analogues of the cellobiose-derived series

should possess several conformations of similar energy, depending on the relative

orientation of the monomeric units [4] along the butadiynediyl moiety, and resulting in

1

corrugated linear or helical shapes. H-NMR studies of the deprotected oligomers of

the glucose-derived series [2] showed no intermolecular association.

We now describe the binomial synthesis of higher oligomers derived from the

partially benzylated cellobiose-derived dialkyne 2, the problems encountered during

acetolytic debenzylation of the tetramer 14, and the synthesis of the mono-, di-, tetra-,

and octamers using acetyl, 4-methoxybenzyl, and silyl instead of benzyl (Bn) protecting

groups. For the preparation of the monomer, we glycosylated an ethynylated b-C-

glucopyranoside by crystalline monoethynylated trichloroacetimidates, and report the

crystal structure analysis of these trichloroacetimidates. We also report a comparison of

physical properties of the deprotected oligomers with those of the glucose-derived

analogues.

Results and Discussion. ± The synthesis of the tetramer 14 started with the

protodesilylation and bromodegermylation [3][4] of the orthogonally protected

monomer 2 [4], yielding exclusively either the dialkyne 3 or the bromoalkyne 4,

respectively (Scheme 1). The bromoalkyne 4 was demethoxymethylated to 5 (HCl in

THF, 92%) to ensure that the partners (3 and 5) for the Cadiot-Chodkiewicz-type cross

coupling [8 ± 11] differ sufficiently in polarity to facilitate the separation of the

heterocoupled from the homocoupled products²). Cross coupling of 3 and 5 under the

conditions developed in the glucose-derived series [3][11] gave 67% of the hetero-

dimer 6, easily separated by chromatography from the homocoupled 7 (2%) and 8

(2%). Continuing with the orthogonal deprotection/activation strategy, the dimer 6

was, on the one hand, fully desilylated to the mono-C-protected alkyne 9 (90%). On the

other hand, 6 was acetylated and bromodegermylated to 10 (91%), again resulting in a

sufficient difference in polarity of the coupling partners. Cross coupling of 9 and 10 as

above yielded 60% of the tetramer 11 together with the homocoupled 12 (2%) and 13

(3%) (Scheme 1)³).

Acetolytic debenzylation is compatible with one glycosidic bond [15]; to check its

compatibility with several glycosidic bonds, we examined the deprotection of the dimer

6 and of the tetramer 14 (Scheme 2). The dimer 6 was deprotected in three steps.

Treatment with 1n aqueous HCl in MeOH at 408 removed both the methoxymethyl-

(MOM) and the Me₃Ge groups to give 76% of the hexol 15. Above 608, one of the

glycosidic bonds was selectively hydrolysed, as evidenced by the isolation of 17 after

2

)

For a successful application of this strategy in the synthesis of cyclodextrin analogues, see [12 ± 14].

Yields of the cross coupling are 20 ± 25% below those for the benzylated glucose-derived oligomers,

carrying C-DOPS and C-GeMe₃groups [3]. TLC showed no evidence for the decomposition of 1 within

48 h under conditions of the cross coupling, but only 80 ± 85% were recovered after chromatography.

Besides the coupling products, polar fractions were obtained by silica-gel chromatography, consisting

(¹H-NMR spectroscopy) of a mixture of unidentified, carbohydrate-derived compounds. The reasons for

the different behaviour of glucose- and cellobiose-derived analogues have been analysed by T. Bohner

(manuscript in preparation), and are related to the nature of the protecting groups.

3

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Scheme 1

a) K₂CO₃in MeOH; 90% [4]. b) CuBr, NBS, acetone, 93% [4]. c) 1n HCl, THF; 92%. d) [Pd₂(dba)₃]/CuI

(dba dibenzylideneacetone), 1,2,2,6,6-pentamethylpiperidine, DMSO; 6 (67%), 7 (2%), 8 (2%). e) K₂CO₃

in MeOH/THF; 90%. f ) 1. Ac₂O, pyridine; 2. NBS, CuBr, acetone; 91%. g) As d); 11 (60%), 12 (2%), 13 (3%).

h) 1n HCl, THF; 74%.

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acetylation of the crude. Acetolytic debenzylation of 15 proceeded best with Me₃SiOTf

(10 mol-%) in Ac₂O yielding only 51% of the dodecaacetate 16⁴). The fully

deprotected dimer 18 was obtained in nearly quantitative yield by deacetylation of

16 (NaOMe in MeOH). This compound is readily soluble in H₂O, MeOH, and

pyridine, but could not be crystallized.

Scheme 2

a) 1n HCl, THF; 76%. b) Ac₂O, Me₃SiOTf; 51%. c) NaOMe, MeOH, Amberlite IR-120 (H ); 95%.

All attempts to fully deprotect tetramer 11 failed. Acid-mediated protodegermy-

lation and demethoxymethylation yielded 74% of 14 (Scheme 1), but the subsequent

acetolysis using Lewis acids (such as Me₃SiOTf, BF₃´ OEt₂, FeCl₃[16], or ZnI₂) in

Ac₂O at various temperatures and concentrations gave mixtures of partially debenzy-

lated products together with unidentified polar material. Thus, we had to avoid Bn

groups.

Cellobiose-derived dialkynes are most efficiently prepared by glycosidation of

monoethynylated glycosyl acceptors with monoethynylated donors [4]. We required a

synthesis of a glycosyl acceptor, and donor, devoid of BnO groups.

The glycosyl acceptor 27 was prepared from 1,6-anhydroglucose (19) (Scheme 3).

Triethylsilylation [17] led to the 2,4-di-O-silyl ether 20 in 90% yield, besides 7% of the

trisilyl ether 21. Retentive ethynylating opening of the 1,3-dioxolane ring of 20 with

lithium (trimethylsilyl)acetylide and freshly sublimed AlCl₃in the presence of 1 equiv.

of 2,4,6-trimethylpyridine gave the C-glucopyranoside 22, which was purified by

distillation and isolated in 68%. This modification of Alzeerꢁs method [1] constitutes

the shortest and highest yielding way to ethynylated b-C-glucopyranosides⁵). The

tetrol 23 was obtained in a nearly quantitative yield by acid-catalyzed desilylation.

4

)

Only ca. 80% of the calculated mass balance of 16 was obtained after chromatography, including elution

with MeOH. ¹H-NMR Data for the polar fractions evidence acetylated carbohydrate and aromatic

residues.

5

)

Exploratory experiments indicate that aryl b-C-glucopyranosides are also available by this procedure.

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Scheme 3

a) Et₃SiCl, 1H-imidazole, DMF; 20 (90%), 21 (7%). b) BuLi, HCꢀCSiMe₃, AlCl₃, 2,4,6-trimethylpyridine,

toluene; 68%. c) 0.1n HCl, THF/MeOH; 95%. d) 4-Methoxybenzaldehyde dimethyl acetal, TsOH ´ H₂O, DMF;

93%. e) 4-Methoxybenzyl trichloroacetimidate, TfOH, Et₂O; 82%. f ) 80% AcOH; 99%. g) TDSCl, 1H-

imidazole, DMF; 95%. h) H₂NNH₂´ HOAc, DMF; 93%. i) K₂CO₃, Cl₃CCN, CH₂Cl₂; 48 h; 85%. j) K₂CO₃,

Cl₃CCN, CH₂Cl₂, 1.5 h; 70%. k) Me₃SiOTf, 4- mol. sieves, CH₂Cl₂; 90%. l) DIBAH, THF; 99%. m) 1.

(Me₃Si)₂NH, Me₃SiCl, CH₂Cl₂; 2. LDA, Me₃GeCl, AcOH/THF/H₂O 1 : 1 : 1; 90%.

Transacetalization of 23 with anisaldehyde dimethyl acetal [18] yielded 93% of the

crystalline 24 that was 4-methoxybenzylated (4-methoxybenzyl trichloroacetimidate,

cat. TfOH [19]) to 25. Hydrolysis of 25 (80% aq. AcOH [20]) gave 26 that was

selectively O-silylated with (thexyl)(dimethyl)silyl chloride ( chlorodimethyl(1,1,2-

trimethylpropyl)silane; TDSCl) [21]. This sequence yielded 84% of the glycosyl

acceptor 27 from 24.

The structure of 23 was established by X-ray analysis⁶) (Fig. 2). The intensities for

23 were recorded at 293 K (R 0.0442). The pyranose ring adopts a ⁴C₁-conformation,

as shown by the endocyclic torsion angles (Table 1). The gg-conformation of the

CH₂OH group is characterized by the endocyclic torsion angles c¹(O(7) C(7)

6

)

Coordinates and thermal parameters were deposited with the Cambridge Crystallographic Data Center, 12,

Union Road, Cambridge CB2 1EZ, UK.

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C(8) O(8)) 67.3(3)8 and c²(C(6) C(7) C(8) O(8)) 53.0(4)8. The ethynyl

substituent is nearly linear (C(1) C(2) C(3) bond angle 177.0(4)8). All bond

lengths are within standard values. Intermolecular H-bonds are found between O(6) ´´´

O(5') (2.725(4) ; 2 x, 0.5 y, 1 z; O(6) H ´´´ O(5') 1.84 ), O(5') ´´´ O(8'')

(2.784(4) ; 1 x,y,z; O(5') H ´´´ O(8'') 2.11 ), and O(8'') ´´´ O(6') (2.747(4) ;

1 x,y,z; O(8'') H ´´´ O(6') 1.79 ) forming a two-dimensional network in the a,b

plane and an infinite chain running along the b axis (Fig. 2). Thus, the cystal structure

of 23 belongs to Class I according to the classification of H-bonding patterns in

monosaccharides by Jeffrey and Saenger [22].

Fig. 2. X-Ray crystal-structure analysis of the tetrol 23: ORTEP [36] presentation (ellipsoids enclose 50% of the

electron density), unit cell (PLUTO [37]), and H-bonding pattern

Table 1. Selected Torsion Angles [8] and Bond Lengths [] in 23. Standard deviations in parentheses.

Torsion Angle [8]

Bond Length []

c¹(O(7) C(7) C(8) O(8))

c²(C(6) C(7) C(8) O(8))

C(3) C(4) C(5) C(6)

C(4) C(5) C(6) C(7)

C(5) C(6) C(7) O(7)

C(6) C(7) O(7) C(3)

C(7) O(7) C(3) C(4)

O(7) C(3) C(4) C(5)

67.3(3)

53.0(4)

53.4(4)

55.0(4)

58.8(3)

64.5(3)

63.7(4)

57.1(4)

C(1) C(2)

C(2) C(3)

C(3) C(4)

C(4) C(5)

C(5) C(6)

C(6) C(7)

C(7) C(8)

C(7) O(7)

1.198(6)

1.466(5)

1.538(5)

1.514(5)

1.520(4)

1.531(4)

1.502(5)

1.449(4)

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Several Ac-protected ethynylated glucopyranosyl donors were examined for the

glycosidation of 27 ⁷). The best results were obtained with the glucopyranosyl

trichloroacetimidates 30 and 31. They were prepared from the known ethynylated

acetate 28 [4] by selective deacetylation with hydrazinium acetate to 29 (93%, a-d/b-d

63 :37) followed by base-catalyzed addition of Cl₃CCN under either thermodynamic or

kinetic control, following Schmidtꢁs procedures [23]. Thus, treatment with Cl₃CCN in

the presence of K₂CO₃in CH₂Cl₂for 48 h gave 85% of 30/31 (88 :12), while the ratio

30/31 was 17:83 after a similar treatment for 1 h. The pure anomers 30 and 31 were

obtained by recrystallization. Glycosidation of the acceptor 27 with either 30 or 31 in

the presence of Me₃SiOTf in CH₂Cl₂at 108 led to the dialkyne 32 in 85 ± 90% yield on

a multigram scale. Deacetylation of 32 with diisobutylaluminium hydride (DIBAH) in

THF [4] yielded 99% of 33, and subsequent trimethylgermylation provided 90% of the

orthogonally protected dialkyne 34 (Scheme 3).

Glycosyl trichloroacetimidates are presumably the most widely used class of

glycosyl donors [24], but so far no solid-state structure of these compounds has been

published. The structure of the pair of anomeric imidates 30 and 31 was determined by

X-ray analysis⁶) (Fig. 3). The intensities for 30 were recorded at 293 K and for 31 at

203 K. Both structures show heavy disorder, which could not be resolved adequately,

especially for 30 (see Exper. Part); the final R values are 0.092 (30) and 0.0573 (31),

respectively. The discussion of bond lengths and angles can, therefore, only point to

trends. Both imidates adopt the ⁴C₁conformation, as shown by the endocyclic torsion

angles (Table 2). The trichloroacetimidoyl group of the a-d-anomer 30 is nearly

anticlinal to the C(1) O(5) bond (Y(O)(5) C(1) O(1) C(9)) 119.1(9)8, whereas,

in the b-d-anomer 31, the torsion angle Y is 83.4(4)8. In both anomers, the imino

group is syn-periplanar to the C(1) O(1) bond (V(C(1) O(1) C(9) N(9))

1(2)8 for 30 and V 4.0(7)8 for 31). Schmidt et al. [25] have calculated the

conformation of the imino group of an a-d-pyranosyl trichloroacetimidate in the gas

phase, and found Y 70 Æ 18 (MM2) or Y 81.38 (MNDO) and V 9 Æ 18 (MM2) or

V 19.88 (MNDO), i.e., significantly differing from the solid-state values of 30 and 31.

The gg-conformation of the AcOCH₂group in 30 is characterized by the endocyclic

torsion angles c¹(O(5) C(5) C(6) O(6)) 68.2(11)8 and c²(C(4) C(5) C(6)

O(6)) 54.5(13)8, while the endocyclic torsion angles c¹ 64.7(4)8 and c²

176.1(3)8 characterize the gt-conformation of the AcOCH₂group in 31. The ethynyl

substituent is nearly linear in both anomers; the bond angles C(4) C(7) C(8) being

178.5(13)8 (30) and 178.4(5)8 (31), respectively.

An anomeric effect in the a-d-anomer 30 is indicated by the shortening of the

C(1) O(5) (1.368(13) ⁸)) and lengthening of the C(1) O(1) (1.448(13) ) bond

(Table 2). Although the conformation of the imidate moiety in the b-d-anomer is close

to the one required for an exo-anomeric effect [26], the length of both C(1) O bonds

(1.423(5) and 1.413(5) ) is in the normal range (Table 2). This is rationalized by the

strong n(O(1)) ! p*(C(9) N) interaction, as supported by the short O(1) C(9)

bond (1.330(5) ).

7

)

Thiophenyl glycoside, phenyltetrazolyl glycoside, glycosyl fluoride, and glycosyl bromide [21].

The shortening is largely an effect of the disorder of the crystal structure.

8

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Fig. 3. X-Ray crystal-structure analysis of 30 and 31: ORTEP [36] presentation (ellipsoids enclose 25% for 30

and 50% for 31 of the electron density) and unit cell (PLUTO [37]). Only one position of the disordered atoms

is shown, arrows indicating the close contacts discussed in the text.

Only approximate intermolecular distances could be obtained for 30 because of the

disordered Cl-atoms and C(3) O/C(6) O acyl groups. The N-atom of 30 is located

3.14(1) away from the neighbouring O(5) (cf. Fig. 3), a value close to the van der

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Table 2. Selected Torsion Angles [8] and Bond Lengths [] in 30 and 31. Standard deviations in parentheses.

Numbering according to Fig. 3.

30

119.1(9)

31

83.4(4)

Y(O(5) C(1) O(1) C(9))

V(C(1) O(1) C(9)N(9))

c¹(O(5) C(5) C(6) O(6))

c²(C(4) C(5) C(6) O(6))

C(1) C(2) C(3) C(4)

C(2) C(3) C(4) C(5)

C(3) C(4) C(5) O(5)

C(4) C(5) O(5) C(1)

C(5) O(5) C(1) C(2)

O(5) C(1) C(2) C(3)

C(1) O(5)

1(2)

4.0(7)

64.7(4)

176.1(3)

53.2(4)

50.8(4)

54.9(4)

65.0(4)

67.7(4)

60.6(4)

1.413(5)

1.423(5)

1.523(5)

1.514(5)

1.330(5)

1.187(7)

68.2(11)

54.5(13)

57.4(11)

57.6(11)

56.7(11)

58.0(11)

56.1(10)

55.9(11)

1.368(13)

1.448(13)

1.51(2)

C(1) O(1)

C(1) C(2)

C(2) C(3)

O(1) C(9)

1.517(14)

1.341(12)

1.16(2)

C(7) C(8)

Waals distance indicating a weak intermolecular H-bond (N H ´´´ O(5) 2.38 ); in

the b-d-anomer 31 the distance of 3.10(1) between the N-atom and the ring O-atom

indicates a intramolecular interaction (N H ´´´ O(5) 2.58 , a(N H ´´´ O)

116(3)8). Both anomers show an intermolecular C_spH ´´´ O H-bond [27][28],

characterized by the distance between C(8) of the a-d-anomer 30 and the C(2) OAc

carbonyl O-atom of 3.24(2) . The shortest intermolecular contact in the b-d-anomer

31 (3.19(1) ) is between C(8) and the C(6) OAc carbonyl O-atom (Fig. 3). Similar

short C_spH ´´´ O contacts have been observed, e.g., in the crystal structures of N-

methylpropiolamide (CSD MPROLA [29]) and (o-chlorobenzoyl)acetylene (CSD

BYACCO [30]). Further evidence for an intermolecular C_spH ´´´ O H-bond derives

from the solid-state (3% KBr) IR spectra of 30 and 31. The wavenumbers for the

1

nÄ(ꢀC H) stretching are significantly lower for 30 (3242 cm ) and 31 (3245 cm ) than

1

for the tetraacetate 28 (3272 cm ). In solution (2% in CCl₄), 30, 31, and 28 show an IR

1

nÄ(ꢀC H) absorption at 3111 cm .

The new cellobiose-derived dialkyne 34 was transformed along similar lines as

described for 2. Protodesilylation of 34 (K₂CO₃/MeOH) yielded 91% of the dialkyne

35, and acetylation followed by CuBr catalyzed bromodegermylation yielded 90% of

the bromoalkyne 36 (Scheme 4).

Cross coupling of 35 and 36 in DMSO under the conditions of Schreiber and co-

workers [31] and Cai and Vasella [11] led to the dimer 37 (66%). Ca. 2% of the trimer

38 was also isolated if the reaction was conducted for 27 h. A control experiment where

the bromoalkyne 36 and the dimer 37 were cross-coupled under the same conditions

showed a very slow transformation into the trimer 38 (marginal amounts were

detectable on TLC after 48 h), possibly due to a CuI-catalyzed degermylation.

Treatment of the dimer 37 with K₂CO₃in MeOH removed the Me₃Si and the Ac

groups, and yielded 78% of the alkyne 39, while treatment with N-bromosuccinimide

(NBS) and CuBr transformed 37 into the bromoalkyne 40 without affecting the other

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Scheme 4

a) K₂CO₃, MeOH/THF; 91%. b) 1. Ac₂O, pyridine; 2. NBS, CuBr, acetone; 90%. c) [Pd₂(dba)₃]/CuI, P(furyl)₃,

Et₃N, DMSO; 65%. d) As a); 78%. e) NBS, CuBr, acetone; 81%. f) Pd₂(dba)₃/CuI, P(furyl)₃, Et₃N, DMSO;

54%. g) K₂CO₃, MeOH/THF; 55%. h) Et₃SiCl, 1H-imidazole, DMF; 92%. i) As e); 86%. j) 1. As f); 2. Ac₂O,

pyridine; 3. HF ´ pyridine, THF, pyridine; 37%.

Helvetica Chimica Acta ± Vol. 81 (1998)

2167

protecting groups. Cross coupling of 39 and 40, similarly as before, gave the tetramer 41

in 54% yield.

Treatment of the tetramer 41 with K₂CO₃in MeOH/THF gave only 55% of the

completely deacetylated and C-desilylated alkyne 42 together with 2% of the

degermylated alkyne 43 and 7% of the partially deacetylated alkyne 44. Obviously,

the concomitant deacetylation and C-desilylation of the tetramer was no longer

selective, marking the limits of the scope of these conditions for the regioselective

deprotection of the prop-2-ynyl ether moiety. To increase the polarity difference

between the coupling partners, the tetramer 41 was first triethylsilylated to 45 (92%)

and then bromodegermylated to 46 (86%). Cross coupling of 42 and 46 required twice

as much of catalyst and phosphine ligand as for the preceding couplings and gave a

mixture containing the desired product which could not be separated by column

chromatography. The crude mixture was, therefore, acetylated, O-desilylated with HF

in pyridine, and separated by chromatography, providing 39% of the octamer 47.

Similarly as observed for the sequential binomial cycles starting with 2, yields

decreased in each cycle and were significantly lower than those realized for the glucose-

derived dialkynes [3].

Deprotection of the tetramer 41 (Scheme 5) required the oxidative cleavage of

the (4-methoxybenzyl)oxy groups with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

( 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile; DDQ) [32], O-de-

silylation with HF in pyridine, and deacetylation to give the deprotected tetramer 48

in 42% overall yield. The deprotected octamer 49 was obtained (34%) from 47 by

treatment with DDQ and deacetylation.

Scheme 5

a) 1. DDQ, CH₂Cl₂/H₂O 9:1; 2. HF ´ pyridine, THF, pyridine; NaOMe, MeOH, Amberlite IR-120 (H ); 42%.

b) 1. DDQ, CH₂Cl₂/H₂O 9 : 1; 2. NaOMe, MeOH, Amberlite IR-120 (H ); 34%.

The deprotected dimer 18, tetramer 48, and octamer 49 are soluble in H₂O, MeOH,

and DMSO, whereas, in the glucose-derived series, only the dimer was soluble in H₂O

and MeOH, the tetramer and the octamer dissolving only in DMSO. The strong

intramolecular C(5') C ´´´ HO C(5) H-bonds within each cellobiose unit were

evidenced for the dimer 18 by the temperature dependence of the chemical shift of

1

the OH resonances (D₆)DMSO, C(5') O ´´´ HO C(5) (Dd/DT 1.65 ppb ´ K ) and

1

C(5''') O ´´´ HO C(7'') (Dd/DT 1.73 ppb ´ K ), but the relative orientation of the

monomeric units around the butydiynediyl bridge could not be deduced. The ¹H-NMR

spectra of the oligomers are almost superimposable; the signals of the cellobiose units

attached to a butadiynediyl unit appearing at slightly lower field (Dd ꢁ 0.05 ± 0.1 ppm)

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than those of the ethynylated residues. Qualitatively, the same behaviour has also been

1

observed for the glucose-derived series. A comparison of selected H-NMR data in

CD₃OD, (D₆)DMSO, and D₂O of the deprotected cellobiose-derived oligomers

(Table 3) shows no evidence for association of these compounds, in agreement with the

observations in the glucose-derived series [2].

Table 3. Selected ¹H-NMR Data (238) of the Deprotected Oligomers. Concentration in parentheses.

1 [4] (n 0; 2.0 ´ 10 ²m)

18 (n 1; 10 ²m)

48 (n 3; 2.0 ´ 10 ³m)

49 (n 7; 5.5 ´ 10 ⁴m)

Solvent

CD₃OD

(D₆)DMSO

3.33

3.85

4.27

2.29

CD₃OD (D₆)DMSO CD₃OD (D₆)DMSO D₂O (D₆)DMSO

a

H

C(1) 2.89

2.88

3.93

4.40

2.47

2.56

3.34

3.86

4.27

2.29

2.97

2.88

3.92

4.41

2.44

2.55

)

2.90

)

C(3) 3.94

3.83

4.26

2.25

2.95

4.11 3.82

4.47 4.27

2.56 2.28

2.59 2.96

C(1^w) 4.40

C(4^w) 2.48

C(8^w) 2.56

2.96

^a) Signal hidden by HDO resonance.

The d(¹³C) values of the propargylic and homopropargylic ethynyl groups of 1 ± 6,

9 ± 11, 15 ± 18, 32 ± 42, 44 ± 46, 48, and 49 are given in Table 4. The assignments of the sꢁs

of CꢀCSiMe₃and CꢀCGeMe₃are in agreement to the values of the analogous

glucose-derived oligomers [2][3]. The sꢁs of the brominated ethynyl groups appear at

significantly higher fields, i.e., at 42.20 ± 44.27 ppm for BrCꢀC and at 75.92 ± 77.97 ppm

for BrCꢀC. The unprotected ethynyl groups show a d at 80.04 ± 82.32 and a s at 73.65 ±

77.97 ppm. The dꢁs for C(3) and C(4^w) resonate at 69.12 ± 72.26 and 35.72 ± 40.08 ppm,

respectively.

We thank the Swiss National Science Foundation and F. Hoffmann-La Roche AG, Basel, for generous

support, and Dr. B. Bernet for checking the experimental part.

Experimental Part

General. Solvents were distilled before use: THF and toluene from Na-benzophenone ketyl, CH₂Cl₂,

MeCN, and MeOH from CaH₂and acetone from CaSO₄. Cl₃CCN was distilled under Ar prior to use. K₂CO₃was

heated until glowing. HCl in aq. MeOH was prepared by mixing 83 ml of HCl (37%) with 917 ml of MeOH.

Reactions were run under Ar or N₂. BuLi was titrated [33] before use. AlCl₃was freshly sublimed and weighted

in a glove-box under N₂. Workup: The mixture was diluted with the indicated solvent and H₂O, the layers were

separated, and the aq. layer was extracted several times with the indicated solvent. The combined org. layers

were washed once with brine, dried (MgSO₄), filtered, and the solvent was removed at 408 under reduced

pressure. Qual. TLC: precoated silica-gel plates (Merck silica gel 60 F₂₅₄), detection by spraying with 5% H₂SO₄

in EtOH followed by heating to ca. 2008. Flash chromatography (FC): silica gel Merck 60 (0.04 ± 0.063 mm).

M.pꢁs: uncorrected. Optical rotations: 1-dm cell at 20 or 258 and 589 nm. FT-IR: 1 ± 2% soln. in the indicated

solvent. ¹H- and ¹³C-NMR: at 200, 300, 400 or 500 MHz; 50, 75, 100, or 125 MHz, resp. MS: Chemical ionization

(CI) with NH₃, fast atom bombardment (FAB), or MALDI-TOF. NOBA: 3-Nitrobenzyl alcohol.

4-C-(Bromoethynyl)-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-

(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (5). A soln. of 4 [4] (1.5 g, 1.64 mmol) in THF (16 ml) was treated

at r.t. with 1m aq. HCl in MeOH (10 ml), heated for 36 h at 408, neutralized with Amberlite IRA-900 (OH

Helvetica Chimica Acta ± Vol. 81 (1998)

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Helvetica Chimica Acta ± Vol. 81 (1998)

form), filtered, and evaporated. FC (hexane/AcOEt 3 : 1 ! 2 : 1 ! 1 : 1) gave 5 (1.18 g, 92%) as a colourless oil.

R_f(toluene/AcOEt 1 : 1) 0.51. [a]²_D⁵ 12.9 (c 1, CHCl₃). IR (CCl₄): 3599s, 3420m (br.), 3090w, 3067m,

3033m, 2961s, 2900s, 2872s, 2182w, 1949w, 1876w, 1758s, 1678w, 1597w, 1550w, 1513w, 1498m, 1454s, 1363s, 1292s,

1251s, 1165s, 1073s, 1028s, 909s, 846s. ¹H-NMR (400 MHz, CDCl₃): 7.40 ± 7.22 (m, 15 arom. H); 4.98 (d, J 10.4,

PhCH); 4.87 (d, J 11.2, PhCH); 4.82 (d, J 11.2, PhCH); 4.78 (d, J 10.4, PhCH); 4.69 (d, J 12.0, PhCH);

4.51 (d, J 12.0, PhCH); 4.39 (d, J 7.8, H C(1')); 4.03 (d, J 9.3, H C(3)); 3.93 (t, J ꢁ 9.4, H C(6)); 3.87

(dd, J 11.8, 3.5, H_aC(8)); 3.77 (dd, J 11.8, 2.3, H_bC(8)); 3.68 ± 3.60 (m, addn. of D₂O ! 3.64, dd, J 12.0,

2.5, H_aC(6'), ! 3.63, dd, J 12.0, 4.6, H_bC(6')); 3.59 (t, J ꢁ 9.4, H C(5)); 3.53 (t, J ꢁ 9.9, H C(4)); 3.45 ±

3.33 (m, addn. of D₂O ! 3.39, br. ddd, J 12.0, 5.0, 2.7, H C(5'), ! 3.37, t, J ꢁ 10.0, H C(3'), exchanged with

D₂O, HO C(2')); 3.18 ± 3.09 (m, addn. of D₂O ! 3.13, t, J ꢁ 8.8, H C(2'), ! 3.13, br. ddd, J ꢁ 11.3, 4.0, 2.5,

H

C(7)); 2.89 (br. d, exchanged with D₂O, J ꢁ 2.2, HO C(3')); 2.41 (t, J ꢁ 10.4, H C(4')); 2.03 (br. s,

exchanged with D₂O, HO C(6')); 0.18 (s, Me₃Si). ¹³C-NMR (100 MHz, CDCl₃): 138.66 (s); 137.89 (s); 137.51

(s); 128.53 (2d); 128.39 (2d); 128.36 (2d); 128.33 (2d); 128.18 (2d); 127.98 (d); 127.87 (d); 127.65 (d); 127.08

(2d); 102.28 (s, CꢀCSi); 102.04 (d, C(1')); 91.50 (s, CꢀCSi); 84.14 (d); 81.94 (d); 78.81 (d); 76.46 (d); 76.13

(s, CꢀCBr); 75.51 (t, PhCH₂); 75.31 (t, PhCH₂); 75.24 (d); 74.75 (d); 74.48 (d); 73.66 (t, PhCH₂); 70.41 (d);

68.33 (t); 62.92 (t); 43.34 (s, CꢀCBr); 37.95 (d, C(4')); 0.30 (q, Me₃Si). FAB-MS (NOBA): 779 (14,

[M(⁸¹Br)] ), 777 (10, [M(⁷⁹Br)] ), 531(6), 307(16), 181(15), 154(64), 91(100). Anal. calc. for C₄₀H₄₇BrO₉Si

(779.80): C 61.61, H 6.07; found: C 61.27, H 6.16.

4-Deoxy-2,3,6-tris-O-(methoxymethyl)-4-C-[2-(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-

anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-deoxy-b-d-

glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-

ynitol (6), 4-C,4'-C-(Buta-1,3-diyne-1,4-diyl)-bis[4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-

benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol] (7), and 4-Deoxy-2,3,6-tris-O-(methoxy-

methyl)-4-C-[2-(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 3)-[4-deoxy-2,3,6-tris-O-(methoxymethyl)-4-

C-[2-(trimethylgermyl)ethynyl-b-d-glucopyranosyl-(1 ! 14)]-1,4,5,12,13,16-hexa-O-benzyl-7,8,9,10-tetradeoxy-

d-erythro-l-galacto-l-gulo-hexadeca-7,9-diynitol (8). To a degassed soln. of 3 (368 mg, 0.42 mmol), 5

(330 mg, 0.42 mmol), [Pd₂(dba)₃] (11.6 mg, 3 mol-%), and CuI (2.0 mg, 3 mol-%) in DMSO (5 ml) was added

1,2,2,6,6-pentamethylpiperidine (PMP; 0.23 ml, 1.35 mmol). The mixture was stirred for 2.5 h at r.t., poured

into ice-cold sat. NH₄Cl soln. (5 ml), and worked up (AcOEt). FC (hexane/AcOEt 3 : 1 ! 2 : 1 ! 1 : 1) gave 6

(443 mg, 67%), 7 (11.5 mg, 2%) and 8 (16 mg, 2%) as colourless oils.

Data of 6: R_f(toluene/AcOEt 1:1) 0.65. [a]²_D⁵ 1.5 (c 1, CHCl₃). IR (CCl₄): 3596m, 3429m (br.),

3090w, 3066m, 3032m, 2899s, 2824m, 2259w, 2173w, 1947w, 1873w, 1807w, 1605w, 1548w, 1497m, 1454s, 1361s,

1292m, 1251s, 1242m, 1213s, 1153s, 1061s, 922m, 908s, 845s. ¹H-NMR (500 MHz, CDCl₃): 7.38 ± 7.22

(m, 30 arom. H); 5.04 (d, J 11.2, PhCH); 4.99 (d, J 10.4, PhCH); 4.93 (d, J 6.4, MeOCH); 4.89 (d, J

6.4, MeOCH); 4.86 (s, PhCH₂); 4.81 (d, J 10.6, PhCH); 4.78 (d, J 10.4, PhCH); 4.76 (d, J 10.6, PhCH);

4.74 (d, J 6.2, MeOCH); 4.70 (d, J 12.0, PhCH); 4.69 (d, J 12.0, PhCH); 4.65 (d, J 6.2, MeOCH); 4.64

(d, J 10.7, PhCH); 4.51 (d, J 12.0, PhCH); 4.52 (d, J 6.5, MeOCH); 4.48 (d, J 6.6, MeOCH); 4.46 (d, J

12.1, PhCH); 4.41 (d, J 7.8, H C(1''')); 4.28 (d, J 7.9, H C(1')); 4.04 (d, J 9.5, H C(5'')); 4.03 (d, J 9.6,

H

C(3)); 3.99 (t, J ꢁ 10.0, H C(8'')); 3.93 (t, J ꢁ 10.0, H C(6)); 3.89 (dd, J 11.4, 3.0, H_aC(6')); 3.83

(dd, J 11.2, 3.2, H_aC(8)); 3.79 ± 3.67 (m, addn. of D₂O ! 3.77, dd, J 11.2, 2.3, H_bC(8), ! 3.75, dd, J ꢁ

11.0, 2.0, H_aC(6'''), ! 3.74, dd, J 10.6, 2.0, H_aC(10''), ! 3.70, dd, J 10.8, 4.6, H_bC(10''), ! 3.68, dd, J

11.0, 5.0, H_bC(6')); 3.61 ± 3.59 (m, addn. of D₂O ! 3.59, dd, J 12.0, 2.5, H_bC(6''')); 3.58 (t, J ꢁ 9.3,

H

C(6'')); 3.55 (t, J ꢁ 9.1, H C(4)); 3.52 (t, J ꢁ 9.0, H C(5)); 3.49 (s, MeO); 3.45 (t, J ꢁ 9.5, H C(7'')); 3.44

(dd, J 10.4, 9.1, H C(3''')); 3.40 ± 3.36 (m, addn, of D₂O ! 3.38, dd, J 10.4, 9.2, H C(3') ! 3.39, br. ddd, J ꢁ

9.7, 5.0, 2.8, H C(5')); 3.36 (s, MeO); 3.30 (ddd, J ꢁ 10.0, 3.2, 2.1, H C(7)); 3.29 (s, MeO); 3.25 (br. s,

exchanged with D₂O, HO C(2')); 3.25 ± 3.20 (m, addn. of D₂O ! 3.23, dd, J 9.1, 8.0, H C(2'), ! 3.22,

ddd, J ꢁ 10.0, 4.5, 2.0, H C(9'')); 3.14 (dd, J 8.9, 7.8, H C(2''')); 3.10 (ddd, J 10.3, 5.5, 2.4, H C(5''')); 2.64

(br. d, J ꢁ 3.0, exchanged with D₂O, HO C(3')); 2.63 (t, J ꢁ 10.5, H C(4''')); 2.52 (t, J ꢁ 10.4, H C(4')); 1.88

(br. t, J ꢁ 6.9, exchanged with D₂O, HO C(6')); 0.34 (s, Me₃Ge); 0.19 (s, Me₃Si). ¹³C-NMR (125 MHz, CDCl₃):

139.01 (s); 138.66 (s); 137.86 (2s); 137.83 (s); 137.44 (s); 128.52 ± 126.97 (several d); 102.26 (s, CꢀCGe); 102.07

(d, C(1')); 101.92 (s, CꢀCSi); 101.62 (d, C(1''')); 97.67 (t, MeOCH₂); 97.62 (t, MeOCH₂); 97.58 (t, MeOCH₂);

91.47 (s, CꢀCSi); 88.71 (s, CꢀCGe); 84.19 (d); 84.03 (d); 81.94 (d); 81.01 (d); 79.41 (d); 78.92 (d); 78.75 (2d);

76.47 (d); 75.56 (t, PhCH₂); 75.50 (t, PhCH₂); 75.47 (d); 75.32 (t, PhCH₂); 75.26 (t, PhCH₂); 75.12 (d); 74.89 (d);

74.71 (d); 74.61 (s); 74.36 (d); 73.69 (t, PhCH₂); 73.55 (t, PhCH₂); 70.40 (d, C(5'')); 70.29 (d, C(3)); 70.18 (s);

68.41 (s); 68.31 (t); 67.98 (t); 67.26 (t); 62.82 (t); 56.60 (q, MeO); 56.33 (q, MeO); 55.19 (q, MeO); 37.94

Helvetica Chimica Acta ± Vol. 81 (1998)

2171

(d, C(4''')); 37.54 (d, C(4')); 0.31 (q, Me₃Si, Me₃Ge); 1s for CꢀC not observed or hidden. MALDI-TOF-MS:

1615 ([M K] ), 1599 ([M Na] ). Anal. calc. for C₈₆H₁₀₆GeO₂₁Si (1576.47): C 65.52, H 6.78; found: C 65.33,

H 6.56.

Data of 7: R_f(toluene/AcOEt 1:1) 0.41. IR (CCl₄): 3595m, 3418m, 3090w, 3068m, 3032m, 2955m, 2875m,

1950w, 1808w, 1740w, 1606w, 1495w, 1455w, 1361m, 1250s, 1212w, 1164m, 1065s, 1030s. MALDI-TOF-MS:

C₈₀H₉₄O₁₈Si₂(1399.80): 1439 ([M K] ), 1423 ([M Na] ).

Data of 8: R_f(hexane/AcOEt 1:1) 0.61. IR (CCl₄): 3090w, 3030w, 2955s, 2928s, 2825m, 1740w, 1640w, 1555w,

1498w, 1455m, 1360m, 1217m, 1155s, 1095s, 1045s. MALDI-TOF-MS: C₉₂H₁₁₈Ge₂O₂₄(1753.13): 1782 ([M

K] ), 1766 ([M Na] ).

4-Deoxy-2,3,6-tris-O-(methoxymethyl)-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-an-

hydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glu-

copyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-d-glycero-d-gulo-oct-1-ynitol (9). A soln. of 6

(158 mg, 0.1 mmol) in THF (2 ml) was treated dropwise at r.t. with cold sat. K₂CO₃soln. in MeOH (0.1 ml),

stirred for 1 h, neutralized with Amberlite IR-120 (H form) filtered, and evaporated. FC (hexane/AcOEt 1 : 1)

gave 9 (136 mg, 90%) as a colourless oil. R_f(toluene/AcOEt 1 : 1) 0.56. [a]²_D⁵ 2.7 (c 1.2, CHCl₃). IR (CCl₄):

3587m, 3429m (br.), 3311m, 3090w, 3066m, 3032m, 2909s, 2824m, 2230w, 2171w, 1947w, 1868w, 1809w, 1603w,

1558w, 1540w, 1497m, 1454s, 1361s, 1293m, 1241m, 1212m, 1154s, 1062s, 922m, 832m. ¹H-NMR (200 MHz,

CDCl₃): 7.40 ± 7.28 (m, 30 arom. H); 5.07 (d, J 11.2, PhCH); 5.02 ± 4.88, 4.87 ± 4.62, 4.54 ± 4.46 (m, 11 PhCH,

6MeOCH); 4.40 (d, J 7.8, H C(1''')); 4.30 (d, J 7.9, H C(1')); 4.06 (br. d, J ꢁ 9.3, H C(5''), H C(3));

4.04 (t, J ꢁ 8.8, H C(8'')); 3.97 (t, J ꢁ 8.6, H C(6)); 3.87 (dd, J 12.0, 2.8, H_aC(6''')); 3.80 ± 3.71 (m, 6 H);

3.68 ± 3.10 (m, 13 H); 3.51 (s, MeO); 3.39 (s, MeO); 3.31 (s, MeO); 3.00 (br. s, HO C(3')); 2.75 (t, J ꢁ 10.4,

H

C(4''')); 2.63 (d, J 2.2, H C(1)); 2.52 (t, J ꢁ 10.5, H C(4')); 2.15 (br. s, HO C(6')); 0.36 (s, Me₃Ge).

¹³C-NMR (75 MHz, CDCl₃): 139.09 (s); 138.39 (s); 137.73 (3s); 137.43 (s); 128.92 ± 126.56 (several d); 102.12

(s, CꢀCGe); 101.87 (d, C(1')); 101.54 (d, C(1''')); 97.56 (t, 2 MeOCH₂); 96.47 (t, MeOCH₂); 88.60 (s, CꢀCGe);

84.14 (d); 83.94 (d); 81.52 (d); 80.91 (d); 80.79 (d, CꢀCH); 79.26 (d); 78.78 (2d); 78.65 (d); 78.52 (d); 76.20 (d);

75.65 (d); 75.49 (t, 2 PhCH₂); 75.38 (d); 75.25 (t, 2 PhCH₂); 75.09 (d); 74.79 (d); 74.62 (d); 74.49 (s, CꢀCH);

74.35 (s); 74.24 (d); 73.46 (t, 2 PhCH₂); 70.20 (d, C(5'')); 69.67 (d, C(3)); 68.25 (s); 68.00 (t); 67.87 (t); 67.15 (t);

62.91 (t); 56.52 (q, MeO); 56.24 (q, MeO); 55.10 (q, MeO); 37.85 (d, C(4''')); 37.56 (d, C(4')); 0.39 (q, Me₃Si,

Me₃Ge); 2s for CꢀC not observed or hidden. MALDI-TOF-MS: 1527 ([M Na] ). FAB-MS (NOBA): 1505

(16, M ), 181(100), 91(100). Anal. calc. for C₈₃H₉₈GeO₂₁(1504.28): C 66.27, H 6.57; found: C 66.04, H 6.50.

4-C-(Bromoethynyl)-4-deoxy-2,3,6-tris-O-(methoxymethyl)-b-d-glucopyranosyl-(1! 8)-5,9-anhydro-6,7,10-

tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-

glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-

ynitol (10). A soln. of 6 (103.3 mg, 65.54 mmol) in CH₂Cl₂(2 ml), pyridine (0.2 ml), and Ac₂O (0.2 ml) was

stirred for 12 h at r.t. and evaporated. The residue was codistilled (toluene) and dried under h.v. for 12 h. A soln.

of the residue (R_f(hexane/AcOEt 5 : 4) 0.33) and NBS (12.25 mg, 68.8 mmol) in acetone (1 ml) was treated with

CuBr (0.94 mg, 10 mol-%), stirred for 4 h at r.t., poured into ice-cold sat. Na₂S₂O₃soln. (3 ml), and worked up

(AcOEt). FC (hexane/AcOEt 3 : 1 ! 2 : 1) gave 10 (98.2 mg, 90%) as a colourless oil. R_f(hexane/AcOEt 1 : 1)

0.71. [a]²_D⁵

5.5 (c 1, CHCl₃). IR (CCl₄): 3090w, 3066m, 3032m, 2954m, 2899m, 2172w, 1946w, 1868w, 1758s,

1700w, 1684w, 1653w, 1635w, 1558w, 1540w, 1497m, 1454m, 1365s, 1292m, 1230s, 1154s, 1117s, 1090s, 1053s, 922m.

¹H-NMR (200 MHz, CDCl₃): 7.40 ± 7.20 (m, 30 arom. H); 5.07 ± 4.59, 4.54 ± 4.36 (m, H C(2'), H C(3'),

12 PhCH, 6 MeOCH); 4.43 (d, J 7.8, H C(1''')); 4.24 (d, J 7.9, H C(1')); 4.22 ± 3.84 (m, 6 H); 3.84 ± 3.62

(m, 5 H); 3.62 ± 3.12 (m, 12 H); 3.49 (s, MeO); 3.36 (s, MeO); 3.29 (s, MeO); 2.79 (t, J ꢁ 10.4, H C(4''')); 2.65

(t, J ꢁ 10.4, H C(4')); 2.00 (s, Ac); 1.95 (s, Ac); 1.91 (s, Ac); 0.17 (s, Me₃Si). ¹³C-NMR (75 MHz, CDCl₃):

170.28 (s, CO); 169.46 (s, CO); 169.30 (s, CO); 139.01 (s); 138.82 (s); 137.86 (s); 137.61 (2s); 137.52 (s);

128.61 ± 127.02 (several d); 102.17 (s, CꢀCSi); 101.46 (d, C(1')); 99.56 (d, C(1''')); 97.51 (t, MeOCH₂); 97.40

(t, MeOCH₂); 96.40 (t, MeOCH₂); 91.08 (s, CꢀCSi); 83.81 (d); 83.68 (d); 81.45 (d); 80.71 (d); 79.19 (d); 78.63

(2d); 78.49 (d); 77.14 (d, CꢀCH); 76.26 (d); 75.44 (t, PhCH₂); 75.36 (d); 75.29 (t, PhCH₂); 75.21 (t, PhCH₂);

74.87 (t, PhCH₂); 74.23 (d); 73.92 (s); 73.55 (t, PhCH₂); 73.43 (t, PhCH₂); 72.23 (2d); 72.01 (d); 70.19

(d, (C(5'')); 70.14 (d, C(3)); 69.70 (s); 68.51 (s); 67.76 (t); 67.49 (t); 66.97 (t); 63.65 (t); 56.21 (q, MeO); 55.01

(q, MeO); 53.68 (q, MeO); 42.37 (s, CꢀCBr); 37.72 (d, C(4''')); 36.15 (d, C(4')); 0.41 (q, Me₃Si); 1s for CꢀC

not observed or hidden. FAB-MS (NOBA): 1688 (17, [M Na] ), 1664 (50, M ), 181(48), 91(100). Anal.

calc. for C₈₉H₁₀₃BrO₂₄Si (1664.77): C 64.21, H 6.24, Br 4.80; found: C 64.34, H 6.19, Br 4.54.

4-Deoxy-2,3,6-tris-O-(methoxymethyl)-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-an-

hydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1! 4-C)-4-deoxy-b-d-gluco-

pyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-

2172

Helvetica Chimica Acta ± Vol. 81 (1998)

(1 ! 4-C)-4-deoxy-2,3,6-tris-O-(methoxymethyl)-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-benzyl-

1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-glucopyra-

nosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol

(11), 4-C,4'-C-(Buta-1,3-diyne-1,4-diyl)-bis[4-deoxy-2,3,6-tris-O-(methoxymethyl)-b-d-glucopyranosyl-(1 ! 8)-

5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-

O-acetyl-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-

d-glycero-d-gulo-oct-1-ynitol] (12), and 4-Deoxy-2,3,6-tris-O-(methoxymethyl)-4-C-[(trimethylgermyl)ethynyl]-

b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetra-deoxy-d-glycero-d-gulo-deca-1,3-di-

ynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 3)-{4-deoxy-2,3,6-tris-O-(methoxymethyl)-4-C-[2-(tri-

methylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glyc-

ero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 14)}-1,4,5,12,13,16-hexa-O-ben-

zyl-7,8,9,10-tetradeoxy-d-erythro-l-galacto-l-gulo-hexadeca-7,9-diynitol (13). A degassed soln. of 9 (85.4 mg,

56.7 mmol), 10 (94.5 mg, 56.73 mmol), [Pd₂(dba)₃] (1.56 mg, 3 mol-%), and CuI (0.32 mg, 3 mol-%) in DMSO

(2 ml) was treated at r.t. with 1,2,2,6,6-pentamethylpiperidine (0.05 ml), stirred for 2.5 h, poured into ice-cold

sat. NH₄Cl soln. (5 ml) and worked up (CH₂Cl₂). FC (hexane/AcOEt 2 : 1) gave 11 (105.2 mg, 60%), 12 (4.1 mg,

2%), and 13 (2.1 mg, 3%) as colourless oils.

Data of 11: R_f(hexane/AcOEt 1:2) 0.26. [a]_D²⁵

13.5 (c 1, CHCl₃). IR (CCl₄): 3706m, 3596m, 3427w

(br.), 3064m, 3032m, 2892s (br.), 2257w, 2170w, 1947w, 1873w, 1758s, 1691w, 1658w, 1640w, 1586m, 1552m,

1513w, 1497m, 1454m, 1365s, 1292s, 1230s, 1154s, 1055s. ¹H-NMR (500 MHz, CDCl₃): 7.40 ± 7.20 (m, 60

arom. H); 5.04 (d, J 11.2, PhCH); 5.01 (d, J 11.3, PhCH); 4.96 (d, J 11.5, PhCH); 4.95 (d, J 11.8, PhCH);

4.93 (d, J 11.2, PhCH); 4.93 (d, J 6.5, MeOCH); 4.90 (d, J 6.5, MeOCH); 4.86 (d, J 6.4, MeOCH);

4.83 ± 4.62 (m, 19 H); 4.61 (d, J 6.2, MeOCH); 4.52 (d, J 6.5, MeOCH); 4.51 (d, J 12.0, PhCH); 4.49

(d, J 6.2, MeOCH); 4.47 (d, J 12.0, PhCH); 4.46 (d, J 6.5, MeOCH); 4.44 (d, J 7.7, H C(1^IV)); 4.42

(d, J 12.0, PhCH); 4.41 (d, J 7.8, H C(1^VIII)); 4.28 (d, J 7.9, H C(1^VI)); 4.23 (d, J 7.9, H C(1^II)); 4.17

(dd, J 12.0, 2.5, 1 H); 4.01 (br. d, J ꢁ 9.5, H C(5^VII), H C(5^V)); 3.99 (d, J 9.6, H C(3^I), H C(5^III));

4.10 ± 3.91 (m, addn. of D₂O ! signal changed, 6 H); 3.76 ± 3.66 (m, addn. of D₂O ! signal changed, 8 H); 3.61 ±

3.52 (m, addn. of D₂O ! 3.59, dd, J ꢁ 11.5, 2.0, H C(6^VI), ! 3.78, br. t, J ꢁ 9.0, 1 H, ! 3.55, t, J ꢁ 8.8, 1 H, !

3.54, br. t, J ꢁ 9.0, 2 H, ! 3.53, t, J ꢁ 8.9, 1 H); 3.49 (s, MeO); 3.44 (s, MeO); 3.37 (s, MeO); 3.35 (s, MeO); 3.29

(s, MeO); 3.25 (s, MeO); 3.48 (dd, J 10.4, 9.1, H C(3^VII)); 3.23 (dd, J 9.1, 7.9, H C(3^VI)); 3.18 (ddd, J

10.1, 4.3, 2.2, H C(7^I)); 3.16 (dd, J 9.1, 7.9, H C(2^VIII)); 3.11 (ddd, J 10.5, 5.5, 2.5, H C(5^VIII)); 3.44 ± 3.20

(m, addn. of D₂O ! signal changed, 12 H); 2.81 (t, J ꢁ 10.6, H C(4^VIII)); 2.74 (t, J ꢁ 10.4, H C(4^IV)); 2.63

(t, J ꢁ 10.5, H C(4^II)); 2.60 (br. s, exchanged with D₂O, HO C(3^VI)); 2.52 (t, J ꢁ 10.4, H C(4^VI)); 2.00

(s, Ac); 1.95 (s, Ac); 1.90 (s, Ac); 1.62 (br. s, exchanged with D₂O, HO C(6^VI)); 0.34 (s, Me₃Ge); 0.17

(s, Me₃Si). ¹³C-NMR (125 MHz, CDCl₃): 170.41 (s, CO); 169.59 (s, CO); 169.44 (s, CO); 139.16 ± 137.40

(several s); 128.72 ± 126.86 (several d); 102.32 (s, CꢀCGe); 102.10 (d, C(1^VI)); 101.93 (s, CꢀCSi); 101.64

(d, C(1^VIII)); 101.52 (d,C(1^IV)); 99.71 (d, C(1^II)); 97.68 (t, 2 MeOCH₂); 97.63 (t, MeOCH₂); 97.56

(t, MeOCH₂); 96.59 (t, 2 MeOCH₂); 91.23 (s, CꢀCSi); 88.72 (s, CꢀCGe); 84.20 (d); 84.05 (d); 83.92 (d);

83.83 (d); 81.81 (d); 81.62 (d); 81.03 (d); 80.88 (d); 79.43 (d); 79.34 (d); 78.93 (2d); 78.86 (d); 78.76 (d); 78.62

(d); 78.47 (d); 77.89 (s); 76.41 (d); 76.35 (d); 76.28 (s); 75.61 (t, PhCH₂); 75.57 (t, 2 PhCH₂); 75.49 (d); 75.38 (d);

75.33 (t, PhCH₂); 75.26 (t, PhCH₂); 75.07 (d); 74.98 (d); 74.67 (d); 74.40 (d); 74.25 (t, PhCH₂); 74.06 (s); 73.96

(s); 73.81 (t, PhCH₂); 73.69 (t, 2 PhCH₂); 73.60 (t, PhCH₂); 73.55 (t, 2 PhCH₂); 72.39 (2d); 72.16 (d); 70.61 (s);

70.42 (d); 70.34 (d); 70.30 (2d); 70.12 (s); 69.86 (s); 68.65 (s); 68.52 (s); 68.22 (t); 67.99 (t); 67.90 (t); 67.67 (t);

67.27 (t); 67.13 (t); 63.78 (t); 62.80 (t); 56.61 (q, MeO); 56.43 (q, MeO); 56.34 (q, 2 MeO); 55.20 (q, 2 MeO);

37.97 (d, C(4^VIII)); 37.58 (d, C(4^VI)); 37.52 (d, C(4^IV)); 36.32 (d, C(4^II)); 20.73 (q, Me); 20.59 (q, Me); 20.57

(q, Me); 0.30 (q, Me₃Si, Me₃Ge); 2s for CꢀC not observed or hidden. MALDI-TOF-MS: 3112 ([M Na] ).

Anal. calc. for C₁₇₂H₂₀₀GeO₄₅Si (3088.15): C 66.88, H 6.56; found: C 66.67, H 6.76.

Data of 12: R_f(hexane/AcOEt 1 :2) 0.68. IR (CCl₄): 3089m, 3066m, 3032m, 2895s (br.), 2183w, 1947w,

1759s, 1605w, 1497m, 1454s, 1366s, 1292m, 1230s, 1153s, 1116s, 1053s. MALDI-TOF-MS: C₁₇₈H₂₀₈O₄₈Si₂

(3171.78): 3195 ([M Na] ).

Data of 13: R_f(toluene/AcOEt 1:2) 0.42. IR (CCl₄): 3590m, 3432m, 3090w, 3065m, 3030m, 2905s, 2825m,

2232w, 1945w, 1865w, 1605w, 1555w, 1542w, 1495m, 1454s, 1360s, 1295m, 1240m, 1155s, 1065s. MALDI-TOF-MS:

C

₁₆₆H₁₉₄Ge₂O₄₂(3006.55): 3029 ([M Na] ).

4-Deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-

glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-

benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-

5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-

Helvetica Chimica Acta ± Vol. 81 (1998)

2173

O-acetyl-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-

d-glycero-d-gulo-oct-1-ynitol (14). A soln. of 11 (68 mg, 19.4 mmol) in THF (1 ml) and 1m aq. HCl in MeOH

(0.5 ml) was stirred for 40 h at 408, neutralized with Amberlite IRA-900 (HO form), filtered, and evaporated.

FC (toluene/AcOEt 1 : 4 ! 1 : 7) gave 14 (39 mg, 74%) as a colourless oil. R_f(AcOEt) 0.72. IR (CHCl₃): 3570s

(br.), 3311m, 3062m, 3032m, 2942s, 2890m, 1755s, 1615m, 1521w, 1446m, 1366m, 1301m, 1260s, 1175w, 1072s,

1

912w. H-NMR (200 MHz, CD₃OD): 7.40 ± 7.21 (m, 60 arom. H); 5.05 ± 4.38 (m, 30 H); 4.05 (d, J ꢁ 9.5, 2 H);

4.00 ± 3.68 (m, 19 H); 3.62 ± 3.20 (m, 25 H); 2.81 (t, J ꢁ 10.4, H C(4^II), H C(4^IV), H C(4^VI)); 2.64 (td, J ꢁ

10.4, 2.0, H C(4^VIII)); 2.15 (d, J 2.1, HCꢀC); 2.02 (s, Ac); 2.01 (s, Ac); 1.99 (s, Ac); 0.18 (s, Me₃Si). MALDI-

TOF-MS for C₁₅₇H₁₆₈O₃₉Si (2707.15): 2730 ([M Na] ).

4-Deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-6,7,10-tri-O-benzyl-1,2,3,4-tetradeoxy-d-gly-

cero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-ben-

zyl-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (15) and 8-O-Acetyl-5,9-anhydro-6,7,10-tri-

O-benzyl-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-

glucopyranosyl-(1 ! 6)-3,7-anhydro-4,5,8-tri-O-benzyl-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-

ynitol (17). A soln. of 6 (22.1 mg, 14.0 mmol) in THF (1 ml) and 1m aq. HCl in MeOH (0.5 ml) was stirred

for 36 h at 408, neutralized with Amberlite IRA-900 (HO form), filtered, and evaporated. FC (toluene/

AcOEt 1 : 2) gave 15 (14.1 mg, 76%) as a colourless oil. In an analogous reaction, 6 (18 mg, 11.4 mmol)

was stirred for 4 h at 408 and 1 h at 60 ± 708. Workup and chromatography gave 15 (9.5 mg, 63%) and a mixture

of the combined other fractions which was acetylated in pyridine (0.5 ml) and Ac₂O (0.5 ml) for 12 h.

Evaporation, co-distillation with toluene, and FC (hexane/AcOEt 3 : 1 ! 2 : 1) gave 17 (1.8 mg, 12%) as a

colourless oil.

Data of 15: R_f(toluene/AcOEt 1:2) 0.23. IR (CHCl₃): 3595m, 3410m (br.), 3307m, 3008m, 2960s, 2910m,

1

2879m, 2840w, 2181w, 1613m, 1514m, 1442m, 1366m, 1301m, 1251s, 1173m, 1075s, 1035s, 912w, 845s. H-NMR

(300 MHz, CDCl₃): 7.40 ± 7.20 (m, 30 arom. H); 5.02 (d, J 10.6, PhCH); 4.94 ± 4.79 (m, 6 PhCH); 4.71 (d, J

11.9, PhCH); 4.68 (d, J 12.1, PhCH); 4.60 ± 4.53 (m, 3 PhCH); 4.41 (d, J 7.6, H C(1')); 4.40 (d, J 7.8,

H

C(1''')); 4.11 (br. d, J ꢁ 9.0, H C(5'')); 4.06 (br. d, J ꢁ 9.0, H C(3)); 3.99 ± 3.89 (m, 3 H); 3.80 ± 3.70

(m, 3 H); 3.70 ± 3.51 (m, 7 H); 3.50 ± 3.22 (m, 7 H); 3.21 ± 3.11 (m, 3 H); 2.53 (t, J ꢁ 10.5, H C(4')); 2.41

(td, J ꢁ 10.5, 2.2, H C(4''')); 2.37 ± 2.30 (m, OH); 2.22 (d, J 2.2, H CꢀC); 2.20 (br. d, OH); 1.86 ± 1.80

(m, OH); 1.68 ± 1.62 (m, OH); 0.21 (s, Me₃Si). ¹³C-NMR (75 MHz, CDCl₃): 138.56 (s); 138.48 (s); 137.86 (s);

137.57 (s); 137.54 (s); 137.49 (s); 128.01 ± 127.13 (several d); 102.21 (s, CꢀCSi); 101.95 (2d, H C(1'),

H

C(1''')); 91.45 (s, CꢀCSi); 80.01 (2d); 81.77 (d); 81.30 (d); 80.04 (d, CꢀCH); 78.86 (d); 78.68 (d); 76.26 (d);

76.14 (s); 75.50 (d); 75.37 (t, 2 PhCH); 75.25 (t, 2 PhCH₂); 75.04 (d); 74.62 (d); 74.51 (d); 74.36 (d); 74.12 (d);

73.61 (s); 73.54 (t, PhCH₂); 73.47 (t, PhCH₂); 72.73 (s, CꢀCH); 70.40 (d); 70.22 (d); 70.11 (d); 68.09 (t); 68.05

(t); 62.73 (t); 61.62 (t); 37.41 (d, C(4')); 36.77 (d, C(4''')); 0.57 (q, Me₃Si); 2s for CꢀC not observed or hidden.

FAB-MS (NOBA): C₇₇H₈₆O₁₈Si (1327.6): 1350.5 (3, [M Na] ), 1327.5 (2, M ), 181(51), 91(100).

Data of 17: R_f(hexane/AcOEt 2 :1) 0.10. IR (CHCl₃): 3307m, 3008m, 2959m, 2910m, 2876m, 2839w, 2182w,

1739s, 1613m, 1581m, 1514m, 1465m, 1367m, 1301m, 1251s, 1173m, 1087s, 1055s, 1035s, 907w, 845s. ¹H-NMR

(500 MHz, C₆D₆, assignment based on H,H-COSY): 7.42 ± 7.05 (m, 30 arom. H); 5.29 (dd, J 9.5, 8.3,

H

C(8'')); 5.27 (t, J ꢁ 9.5, H C(3')); 5.10 (d, J 10.5, PhCH); 5.00 (dd, J 9.1, 7.8, H C(2')); 4.97 (d, J

11.0, PhCH); 4.87 (d, J 11.0, PhCH); 4.76 (d, J 10.5, PhCH); 4.73 (d, J 12.0, PhCH); 4.70 (d, J 12.0,

PhCH); 4.66 (d, J 7.9, H C(1')); 4.63 (d, J 11.0, PhCH); 4.59 (d, J 12.0, PhCH); 4.54 (d, J 12.1, PhCH);

4.33 (d, J 12.1, PhCH); 4.30 (d, J 12.1, PhCH); 4.23 (d, J 12.0, PhCH); 4.20 (dd, J 12.0, 2.7, H_aC(6'));

4.14 (dd, J 12.0, 4.7, H_bC(6')); 4.12 (t, J ꢁ 9.5, H C(6)); 3.99 (d, J 9.4, H C(3)); 3.87 (dd, J 9.3, 0.5,

H

C(5'')); 3.74 (dd, J 11.0, 3.0, H_aC(8)); 3.59 (t, J ꢁ 9.5, H C(4)); 3.58 (dd, J 10.9, 1.2, H_bC(8)); 3.54

(dd, J 11.5, 3.5, H_aC(10'')); 3.46 (dd, J 10.9, 5.0, H_bC(10'')); 3.44 (t, J ꢁ 9.3, H C(6'')); 3.40 (t, J ꢁ 9.2,

H

C(5)); 3.33 (t, J ꢁ 9.0, H C(7'')); 3.23 (ddd, J 9.7, 5.0, 3.5, H C(9'')); 3.08 (ddd, J 10.5, 4.6, 2.6,

C(5')); 2.97 (ddd, J 10.0, 3.0, 1.2, H C(7)); 2.72 (t, J ꢁ 10.5, H C(4')); 1.74 (s, Ac); 1.73 (s, Ac); 1.57

(s, Ac); 1.54 (s, Ac); 0.11 (s, Me₃Si). ¹³C-NMR (125 MHz, C₆D₆): 169.81 (s, CO); 169.48 (s, CO); 169.02

(s, CO); 168.93 (s, CO); 140.05 (s); 139.10 (2s); 138.63 (s); 138.58 (s); 138.42 (s); 128.98 ± 127.46 (several d);

103.99 (s, CꢀCSi); 100.43 (d, C(1')); 90.64 (s, CꢀCSi); 84.03 (d); 83.53 (d); 82.36 (d); 81.78 (d); 79.27 (d); 77.94

(d); 77.13 (d); 75.89 (s); 75.60 (t, PhCH₂); 75.56 (t, PhCH₂); 75.27 (s); 75.12 (t, PhCH₂); 74.98 (t, PhCH₂); 73.91

(t, PhCH₂); 73.78 (t, PhCH₂); 72.87 (2d); 72.58 (d); 70.87 (d); 70.75 (d); 70.44 (d); 70.37 (s); 70.09 (t); 68.99 (s);

68.29 (t); 63.86 (t); 36.92 (d); 20.49 (q, Me); 20.45 (q, Me); 20.21 (q, Me); 20.19 (q, Me); 0.30 (q, Me₃Si).

FAB-MS (NOBA): C₇₇H₈₄O₁₈Si (1324.5): 1347 (14, [M Na] ), 1324 (9, M ), 181(12), 91(100).

2,3,6-Tri-O-acetyl-4-deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 8)-6,7,10-tri-O-acetyl-5,9-anhydro-1,2,3,4-

tetradeoxy-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-glucopyranosyl-

2174

Helvetica Chimica Acta ± Vol. 81 (1998)

(1 ! 6)-4,5,8-tri-O-acetyl-3,7-anhydro-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (16).

A

soln. of 15 (16.2 mg, 12.2 mmol) in Ac₂O (1 ml) was treated at 08 dropwise with Me₃SiOTf (0.1ml), stirred

for 12 h at 48, poured into ice-cold sat. NaHCO₃soln. (5 ml), stirred for 1 h, and worked up (AcOEt). FC

(hexane/AcOEt 2 : 1 ! 1 : 1 ! 1 : 2) gave 16 (8.1 mg, 51%) as a white solid. R_f(hexane/AcOEt 1 : 1) 0.18. M.p.

260 ± 2628. [a]²_D⁵

9.4 (c 0.8, CHCl₃). IR (CCl₄): 3307m, 2956m, 2860m, 2122w, 1755s, 1601w, 1430m, 1386s,

1302m, 1248s, 1167m, 1050s, 975w, 951w, 901w, 848m. ¹H-NMR (500 MHz, C₆D₆, assignment based on H,H-

COSY): 5.36 (t, J ꢁ 9.7, H C(4)); 5.33 (dd, J 10.9, 9.3, H C(3')); 5.26 (t, J ꢁ 9.7, H C(6'')); 5.234 (dd, J

10.9, 9.3, H C(3''')); 5.23 (t, J ꢁ 9.3, H C(5)); 5.19 (t, J ꢁ 9.3, H C(7'')); 4.95 (dd, J 9.3, 7.9, H C(2')); 4.90

(dd, J 9.3, 7.9, H C(2''')); 4.44 (dd, J 11.8, 1.8, H_aC(8)); 4.42 (dd, J 11.8, 1.7, H_aC(10'')); 4.29 (dd, J

12.2, 2.3, H_aC(6''')); 4.23 (dd, J 12.1, 5.2, H_bC(6''')); 4.17 (d, J 7.9, H C(1')); 4.13 (d, J 8.0, H C(1'''));

4.12 (d, J 4.6, 2 H C(6')); 4.02 (dd, J 11.7, 6.5, H_bC(8)); 4.00 (dd, J 11.6, 6.5, H_bC(10'')); 3.92 (d, J

9.9, H C(3)); 3.85 (dd, J 9.8, 0.6, H C(5'')); 3.43 (t, J ꢁ 9.5, H C(6)); 3.40 (t, J ꢁ 9.4, H C(8'')); 3.26

(ddd, J 10.5, 5.1, 2.2, H C(5''')); 3.08 (dt, J ꢁ 10.3, 3.9, H C(5')); 3.06 (ddd, J 10.1, 6.5, 2.0, H C(7)); 3.04

(ddd, J 10.2, 6.6, 1.9, H C(9'')); 2.57 (td, J ꢁ 10.5, 2.4, H C(4''')); 2.56 (t, J ꢁ 10.5, H C(4')); 1.95 (s, Ac);

1.92 (s, Ac); 1.88 (s, Ac); 1.87 (s, Ac); 1.86 (s, Ac); 1.83 (s, Ac); 1.78 (s, Ac); 1.77 (s, Ac); 1.68 (d, J 2.4,

H

CꢀC); 1.67 (s, Ac); 1.66 (s, Ac); 1.62 (s, Ac); 1.60 (s, Ac); 0.06 (s, Me₃Si). ¹³C-NMR (125 MHz, C₆D₆):

170.06 (s, CO); 170.03 (s, CO); 169.87 (s, CO); 169.76 (s, CO); 169.51 (s, CO); 169.49 (s, CO);

169.34 (s, CO); 169.33 (s, CO); 169.22 (s, CO); 169.19 (s, CO); 169.12 (s, CO); 169.03 (s, CO);

101.41 (d, C(1')); 101.32 (d, C(1''')); 100.57 (s, CꢀCSi); 92.32 (s, CꢀCSi); 78.29 (d, CꢀCH); 77.29 (d); 77.05

(d); 77.01 (d); 76.90 (d); 75.79 (s); 73.61 (2d); 73.45 (s); 73.35 (s, CꢀCH); 73.00 (2d); 72.67 (d); 72.52 (d); 72.43

(d); 72.37 (d); 72.31 (d); 71.77 (d); 70.87 (s); 69.12 (d); 68.85 (d); 68.76 (s); 63.90 (t); 63.81 (t); 62.97 (t); 62.83

(t); 36.57 (d, C(4')); 35.66 (d, C(4''')); 20.60 (q, Me); 20.49 (q, Me); 20.43 (q, Me); 20.38 (q, Me); 20.35 (q, Me);

20.25 (q, Me); 20.22 (q, 3 Me); 20.18 (q, Me); 20.17 (q, Me); 20.10 (q, Me); 0.53 (q, Me₃Si). FAB-MS

(NOBA): 1291 (21, [M 1] ), 977(12), 905 (100, [M aglycone] ), 845(17), 369(29), 297(48), 237(14),

195(78), 154(92). Anal. calc. for C₅₉H₇₃O₃₀Si (1290.29): C 54.92, H 5.70; found: 54.74, H 5.66.

4-Deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-d-glycero-d-gulo-deca-

1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-d-glycero-d-gulo-oct-

1-ynitol (18). A soln. of 16 (12.3 mg, 9.5 mmol) in MeOH (2 ml) was treated with 0.1m NaOMe in MeOH

(0.2 ml) stirred for 3 h at r.t., neutralized with Amberlite IR-120 (H form), filtered, and evaporated. Drying for

24 h under h.v. gave 18 (6.8 mg, quant.) as a colourless oil. R_f(AcOEt/MeOH/H₂O 10 : 3 : 2) 0.39. IR (KBr):

3415s (br.), 2915w, 2126w, 1638m, 1425m, 1371m, 1305m, 1160m, 1090s, 1040s. ¹H-NMR (300 MHz, CD₃OD):

4.41 (d, J 7.8, H C(1')); 4.40 (d, J 7.8, H C(1''')); 4.03 (d, J 9.5, H C(5'')); 3.93 (dd, J 9.5, 2.0,

H

C(3)); 3.92 (dd, J ꢁ 11.5, 3.0, H_aC(6')); 3.90 ± 3.84 (m, H_aC(8), H_aC(6'''), H_aC(10'')); 3.82 (dd, J ꢁ

12.0, 3.8, H_bC(8)); 3.72 (dd, J 11.5, 6.0, H_bC(6')); 3.70 (dd, J 11.2, 5.2, H_bC(6''')); 3.61 (dd, J ꢁ 11.0, 2.0,

H_bC(10'')); 3.56 (br. t, J ꢁ 9.5, H C(5)); 3.54 (br. t, J ꢁ 9.4, H C(7'')); 3.53 (br. t, J ꢁ 9.3, H C(3'),

H

C(3''')); 3.45 (t, J ꢁ 10.6, H C(6), H C(8'')); 3.39 ± 3.37 (m, H C(7), H C(5'), H C(5'''), H C(9''));

3.36 (br. t, J ꢁ 9.5, H C(4), H C(6'')); 3.14 (t, J ꢁ 10.5, H C(2'), H C(2''')); 2.88 (d, J 2.0, HCꢀC C(3));

2.63 (t, J ꢁ 10.5, H C(4')); 2.56 (d, J 2.1, HCꢀC C(4''')); 2.47 (td, J ꢁ 10.4, 2.1, H C(4''')). ¹H-NMR

(500 MHz, (D₆)DMSO, assignment based on H,H-COSY): 5.64 (d, J 6.0, exchanged with D₂O, HO C(6''));

5.52 (d, J 6.1, exchanged with D₂O, HO C(3')); 5.47 (d, J 6.0, exchanged with D₂O, HO C(4)); 5.42

(d, J 4.9, exchanged with D₂O, HO C(2')); 5.34 (d, J 4.9, exchanged with D₂O, HO C(2''')); 5.32 (d, J

6.1, exchanged with D₂O, HO C(3''')); 4.87 (t, J ꢁ 5.5, exchanged with D₂O, HO C(10'')); 4.78 (dd, J 6.0, 5.5,

exchanged with D₂O, HO C(8)); 4.67 (d, J 1.6, exchanged with D₂O, HO C(7'')); 4.62 (t, J 5.6, exchanged

with D₂O, HO C(6''')); 4.59 (t, J 5.4, exchanged with D₂O, HO C(6')); 4.58 (d, J 1.7, exchanged with D₂O,

HO C(5)); 4.30 (d, J 7.9, H C(1')); 4.27 (d, J 8.0, H C(1''')); 4.01 (d, J 9.5, H C(5'')); 3.86 (dd, J 9.7,

2.0, H C(3)); 3.73 ± 3.62 (m, addn. of D₂O ! br. d, J ꢁ 11.2, H_aC(6'''), H_aC(6'), H_aC(8), ! 3.66 br. d, J ꢁ

10.0, H_aC(10'')); 3.59 ± 3.52 (m, addn. of D₂O ! 3.57, br. dd, J ꢁ 12.0, 5.0, H_bC(6'), H_bC(6''')); 3.51 ± 3.45

(m, addn. of D₂O ! signal changed, H_bC(8), H_bC(10''), H C(5')); 3.42 ± 3.24 (m, addn. of D₂O ! 3.42,

ddd, J ꢁ 10.2, 6.0, 2.0, H C(5'''), ! 3.38, t, J ꢁ 9.2, H C(6), ! 3.37, t, J ꢁ 9.2, H C(8''), ! 3.31, dd, J 10.3,

9.0,

H

C(3'), additionally

H

C(7),

H

C(9''),

H

C(3'''),

H

C(7''),

H

C(5)); 3.34 (d, J 2.0,

CꢀC C(3)); 3.16 (br. td, J ꢁ 9.0, 6.0, addn. of D₂O ! t, J ꢁ 8.6, H C(6'')); 3.14 (br. td, J ꢁ 9.0, 6.2, addn.

of D₂O ! t, J ꢁ 8.7, H C(4)); 2.97 (d, J 2.2, H CꢀC C(4''')); 2.93 (br. td, J ꢁ 9.0, 4.0, addn. of D₂O ! t, J ꢁ

8.4, H C(2')); 2.92 (br. td, J ꢁ 9.0, 4.0, addn. of D₂O ! t, J ꢁ 8.5, H C(2''')); 2.52 (t, J ꢁ 10.3, H C(4')); 2.29

(td, J ꢁ 10.5, 2.2, H C(4''')). ¹³C-NMR (125 MHz, (D₆)DMSO): 102.82 (d, C(1')); 102.77 (d, C(1''')); 82.22

(d, HCꢀC C(4''')); 81.92 (d, HCꢀC C(3)); 79.77 (d); 79.67 (d); 78.92 (s); 78.79 (d); 78.67 (d); 75.87

(s, HCꢀC C(3)); 75.71 (d); 75.62 (d); 75.59 (s); 75.28 (d); 74.82 (d); 74.12 (d); 73.84 (d); 73.81 (d); 73.75 (d);

73.70 (s, HCꢀC C(4''')); 73.27 (d); 73.16 (d); 70.07 (d); 69.75 (d); 69.22 (s); 66.57 (s); 61.65 (t); 61.59 (t); 60.09

Helvetica Chimica Acta ± Vol. 81 (1998)

2175

(2t); 37.78 (d, C(4''')); 37.11 (d, C(4')). ESI-MS: 737.2 (100, [M Na] ), 732.4 (56, [M Na] ). MS-MS of m/z

732 ([M Na] ): 715 (56, [M 1] ), 545 (42, [M NH₄C₈H₁₁O₅] ), 527 (50, [M C₈H₁₁O₅] ), 357

(100, M ).

1,6-Anhydro-2,4-bis-O-(triethylsilyl)-b-d-glucopyranose (20) and 1,6-Anhydro-2,3,4-tris-O-(triethylsilyl)-b-

d-glucopyranose (21). A soln. of 1,6-anhydroglucose (19; 2.35 g, 14.5 mmol) in pyridine (5 ml) and CH₂Cl₂

(10 ml) was treated at 08 dropwise with Et₃SiCl (4.99 ml, 29.7 mmol) ( ! white suspension), stirred for 25 min,

diluted with hexane (50 ml), washed twice with 1m HCl, dried (MgSO₄), filtered, and evaporated. FC

(hexane ! hexane/AcOEt 20 : 1 ! 10 : 1) gave 21 (511 mg, 7%) and 20 (5.1 g, 90%) as colourless oils.

Data of 20: R_f(hexane/AcOEt 3 :1) 0.53. [a]_D²⁵

24.7 (c 1.1, CHCl₃). IR (CCl₄): 3621w, 3567w, 2955s,

2899m, 2877s, 1458m, 1414m, 1380w, 1327w, 1239m, 1106s, 1077s, 1017s, 973m, 895m. ¹H-NMR (200 MHz,

CDCl₃): 5.30 (br. s, H C(1)); 4.40 (br. d, J ꢁ 4.6, H C(5)); 3.88 (dd, J 7.5, 0.8, H_endoC(6)); 3.68 (dd, J 7.5,

5.4, H_exoC(6)); 3.55 ± 3.44 (m, H C(2), H C(3), H C(4)); 2.11 (d, J 5.4, HO C(3)); 0.98 (t, J 7.9, 2

(MeCH₂)₃Si); 0.65 (q, J 7.9, 2 (MeCH₂)₃Si). ¹³C-NMR (50 MHz, CDCl₃): 103.50 (d, C(1)); 78.05 (d); 75.67

(d); 73.99 (d); 73.67 (d); 66.30 (t); 6.57 (6q); 4.57 (3t); 4.50 (3t). CI-MS: 408.3 (16, [M NH₄] ), 391 (100,

[M 1] ), 373(6), 343(6), 315(50), 301(46), 288(8), 276(5), 259(17), 241(6), 229(18), 211(6), 199(7),

183(12), 171(21), 157(16), 145(10), 132(19), 115(13), 103(12), 75(3), 49(9). Anal. calc. for C₁₈H₃₈O₅Si₂

(390.67): C 55.34, H 9.80; found: C 55.25, H 9.71.

Data of 21: R_f(hexane/AcOEt 3 :1) 0.90. [a]_D²⁵

24.7 (c 1.1, CHCl₃). ¹H-NMR (200 MHz, CDCl₃): 5.28

(br. s, H C(1)); 4.37 (br. d, J ꢁ 4.3, H C(5)); 4.09 (dd, J 6.4, 0.9, H_endoC(6)); 3.70 ± 3.58 (m, H_exoC(6),

H

C(2)); 3.49 (br. s, H C(3)); 3.43 (br. d, J ꢁ 1.2, H C(4)); 0.98 (t, J ꢁ 7.9, 3 (MeCH₂)₃Si); 0.70 ± 0.56

(m, 3 (MeCH₂)₃Si). ¹³C-NMR (50 MHz, CDCl₃): 102.20 (d, C(1)); 77.56 (d); 75.19 (d); 72.84 (d); 71.86 (d);

64.56 (t); 6.60 (6q); 6.53 (3q); 4.66 (3t); 4.59 (6t). CI-MS: 522 (4, [M NH₄] ), 505 (28, [M 1] ), 475(11),

459(20), 429(12), 373(95), 343(16), 327(14), 315(10), 301(100), 288(75), 275(11), 259(11), 241(14),

199(17), 183(5), 157(6), 145(5), 132(44), 115(16).

3,7-Anhydro-1,2-dideoxy-4,6-bis-O-(triethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (22). A

soln. of (trimethylsilyl)acetylene (16.8 ml, 0.12 mol) in toluene (100 ml) was treated at 158 dropwise with

1.52m BuLi in hexane (79 ml, 0.12 mol) ( ! white suspension), stirred for 30 min at r.t., diluted with THF (5 ml)

( ! clear soln.), and added dropwise at 108 to a suspension of freshly sublimed AlCl₃(16 g, 0.12 mol) in

toluene (75 ml). The suspension was stirred at r.t. for 1 h ( ! viscous slightly yellow suspension), heated to 608,

treated with a soln. of 20 (11.65 g, 0.03 mol) and 2,4,6-trimethylpyridine (4.3 ml, 0.033 mol) in toluene (20 ml)

dropwise over 1 min, and heated for 70 min at 1308 ( ! black soln.). The mixture was cooled to 08, poured

carefully into ice-cold H₂O/1m aq. HCl 2 : 1 (200 ml) and worked up (AcOEt). Bulb-to-bulb distillation (1608/

0.1 Torr) of the resulting black oil gave 22 (11.3 g, 77%). Slightly yellow oil. R_f(hexane/AcOEt 3 : 1) 0.61. IR

(CCl₄): 3606m, 2957s, 2912s, 2892m, 2877s, 2180w, 1742w, 1458m, 1414m, 1379m, 1285m, 1251s, 1214w, 1147s,

1

1107s, 1090s, 1057s, 1034m, 1015m, 1004s, 917w, 846s. H-NMR (200 MHz, CDCl₃): 3.94 (d, J 9.1, H C(3));

3.86 (ddd, J 11.5, 7.1, 2.8, H_aC(8)); 3.67 (ddd, J 11.5, 6.5, 5.7, H_bC(8)); 3.50 (t, J ꢁ 8.6, H C(4)); 3.49

(t, J ꢁ 8.7, H C(6)); 3.34 (td, J ꢁ 8.4, 2.9, H C(5)); 3.26 (br. ddd, J ꢁ 9.0, 5.7, 2.8, H C(7)); 2.15 (d, J 2.9,

HO C(5)); 2.01 (br. d, J ꢁ 6.6, HO C(8)); 0.95 ± 1.10 (m, 2 (MeCH₂)₃Si); 0.62 ± 0.80 (m, 2 (MeCH₂)₃Si); 0.21

(s, Me₃Si). ¹³C-NMR (50 MHz, CDCl₃): 102.52 (s, CꢀCSi); 91.03 (s, CꢀCSi); 80.37 (d, C(5)); 79.41 (d, C(6));

75.29 (d, C(4)); 71.54 (d, C(7)); 71.00 (d, C(3)); 62.18 (t, C(8)); 6.87 (3q); 6.78 (3q); 5.35 (3t); 5.10 (3t); 0.36

(q, Me₃Si). CI-MS: 506 (11, [M NH₄] ), 489 (100, [M 1] ), 459(5), 399(5), 357(11), 327(13), 309(6),

281(8), 268(17), 255(22), 241(13), 201(10), 145(4), 120(16).

3,7-Anhydro-1,2-dideoxy-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (23). A soln. of 22 (15.7g,

32.15 mmol) in MeOH/H₂O/AcOH 1:1:1 was stirred for 1 h at 408, evaporated, and co-distilled (toluene). The

resulting yellow oil was crystallized from acetone/heptane to give 23 (5.1 g, 61%) as colourless needles. FC of the

mother liquor (CHCl₃/MeOH 10 :1) gave another 2.5 g (30%) of 23 as a white solid (total 7.6 g, 91%).

R_f(CHCl₃/MeOH 9 :1) 0.20. M.p. 148 ± 1498. [a]²_D⁵ 6.7 (c 1, MeOH). IR (KBr): 3567s, 3406s (br.), 2958s,

2929s, 2178m, 1751w, 1630w, 1458m, 1383m, 1363w, 1304w, 1250s, 1190w, 1078s, 1015s, 978m, 843s. ¹H-NMR

(200MHz, CD₃OD): 3.90 (d, J 9.6,

H

C(3)); 3.88 (dd, J 11.8, 1.6, H_aC(8)); 3.84 (br. d, J ꢁ 11.6,

H_bC(8)); 3.35 ± 3.24 (m, H C(4), H C(5), H C(6), H C(7)); 0.14 (s, Me₃Si). ¹³C-NMR (50 MHz,

CD₃OD): 103.98 (s, CꢀCSi); 82.08 (d); 79.29 (d); 75.26 (d); 72.46 (d); 71.38 (d, C(3)); 62.84 (t, C(8)); 0.21

(q, Me₃Si); 1d for C(1) not observed or hidden. CI-MS: 278 (55, [M NH₄] ), 261 (9, [M 1] ), 238(3),

227(5), 209(10), 195(13), 180(14), 163(18), 90(100), 74(19). Anal. calc. for C₁₁H₂₀O₅Si (260.36): C 50.75,

H 7.74; found: C 50.72, H 7.92.

X-Ray Analysis of 23. Crystals were obtained by isothermic distillation of heptane into a ca. 10% soln. of 23

in acetone. C₁₁H₂₀O₅Si (260.36), monoclinic, P2₁, a 6.126(1) , b 6.152(2) , c 18.478(5) , b 96.11(2)8,

2176

Helvetica Chimica Acta ± Vol. 81 (1998)

V 692.4 ³, Z 2, D_calc. 1.249 Mg/m³. The intensities were recorded on an Enraf-Nonius-CAD-4 diffrac-

tometer (graphite monochromator, CuK_a, l 1.54184 ) at 293(2) K. Of the 1400 total collected reflections,

1287 were independent. The structure was solved with direct methods (SHELXS86 [34]). The non-H-atoms

were refined anisotropically with SHELXL92 [35]. The H-atoms were obtained from a difference Fourier map

and refined isotropically. The final R value using 1221 reflections with I > 3s(I) was 0.0442.

3,7-Anhydro-1,2-dideoxy-6,8-O-(4-methoxybenzylidene)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol

(24). A soln. of 23 (7.6 g, 29.23 mmol) and anisaldehyde dimethyl acetal (6.6 ml, 35 mmol) in MeCN (170 ml)

was treated with TsOH ´ H₂O (277 mg, 5 mol-%), stirred at r.t. for 1 h ( ! dark-violet soln.), treated with Et₃N

(0.3 ml) ( ! yellow soln.), and evaporated. FC (100 g of Si-60, CH₂Cl₂/toluene/Et₃N 1 : 1 : 0.01 ! CH₂Cl₂/

toluene/MeOH/Et₃N 20 : 1 : 1 : 0.01) gave 24 (11.06 g, 92%) as a colourless oil. An anal. sample was crystallized

from AcOEt/heptane. R_f(hexane/AcOEt 1 : 1) 0.25. M.p. 1548. [a]²_D⁵ 15.7 (c 1, CHCl₃). IR (CCl₄): 3608m,

3457w (br.), 2960m, 2901m, 2178w, 1741w, 1616m, 1589m, 1518m, 1465w, 1383m, 1303m, 1251s, 1172m, 1113s,

1095m, 1054m, 1039m, 1012m, 973m, 926w, 846m. ¹H-NMR (200 MHz, CDCl₃): 7.47 ± 7.40 (m, 2 arom. H);

6.95 ± 6.90 (m, 2 arom. H); 5.51 (s, ArCH); 4.36 (dd, J 10.4, 4.6, H_eqC(8)); 4.13 (d, J 9.1, H C(3)); 3.83

(s, MeO); 3.80 (td, J ꢁ 10.8, 2.5, H C(5)); 3.72 (td, J ꢁ 9.1, 2.9, H C(4)); 3.61 ± 3.41 (m, H C(6), H C(7),

H_axC(8)); 2.73 (d, J 2.1, HO C(5)); 2.51 (d, J 2.9, HO C(4)); 0.14 (s, Me₃Si). ¹³C-NMR (50 MHz,

CDCl₃): 160.29 (s); 129.41 (s); 127.66 (2d); 113.73 (2d); 101.73 (d); 100.62 (s, CꢀCSi); 92.36 (s, CꢀCSi); 82.27

(d); 74.24 ± 73.89 (m); 71.48 (d); 70.49 (d); 68.43 (t, C(8)); 55.19 (q, MeO); 0.39 (q, Me₃Si). CI-MS: 379 (22,

[M 1] ), 137(100), 121(44), 90(18), 74(5), 35(33). Anal. calc. for C₁₉H₂₆O₆Si (378.50): C 60.29, H 6.92;

found: C 60.22, H 6.97.

3,7-Anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-6,8-O-(4-methoxybenzylidene)-1-C-(trimethylsil-

yl)-d-glycero-d-gulo-oct-1-ynitol (25). A soln. of 24 (108 mg, 0.285 mmol) and 4-methoxybenzyl trichloroacet-

imidate [19] (166 mg, 0.588 mmol) in THF/Et₂O 1:1 (5 ml) was treated at 08 dropwise with a 0.05m soln. of

TfOH in Et₂O (0.17 ml, 3 mol-%), stirred for 1 h, neutralized with Amberlite IRA-900 (OH form), filtered, and

evaporated. FC (hexane/AcOEt/Et₃N 6 :1:0.05) gave 25 (144.6 mg, 82%) as a colourless oil. R_f(hexane/

AcOEt) 0.74. [a]_D²⁵ 21.2 (c 1.0, CHCl₃). IR (CCl₄): 3001w, 2956m, 2935m, 2907m, 2872m, 2836m, 2183w,

1614m, 1587w, 1515s, 1464m, 1441w, 1382m, 1367m, 1250s, 1172m, 1101s, 1042s, 1003m, 928w, 846s. ¹H-NMR

(300 MHz, CDCl₃): 7.41 ± 7.21 (m, 6 arom. H); 6.91 ± 6.82 (m, 6 arom. H); 5.51 (s, ArCH); 4.88 (d, J 10.4,

ArCH); 4.84 (d, J 11.1, ArCH); 4.76 (d, J 10.3, ArCH); 4.71 (d, J 10.9, ArCH); 4.34 (dd, J 10.6, 5.0,

H_eqC(8)); 4.15 (d, J 8.7, H C(3)); 3.81 (s, MeO); 3.80 (s, MeO); 3.79 (s, MeO); 3.80 ± 3.61 (m, H C(4),

H

C(5), H C(6), H_eqC(8)); 3.43 ± 3.32 (m, H C(7)); 0.21 (s, Me₃Si). ¹³C-NMR (50 MHz, CDCl₃): 160.10

(s); 159.46 (s); 159.31 (s); 130.71 (s); 130.26 (s); 129.85 (2d); 129.69 (2d); 127.31 (2d); 113.79 (4d); 113.57 (2d);

102.04 (s, CꢀCSi); 101.06 (d, ArCH); 91.38 (s, CꢀCSi); 81.64 (d); 81.44 (d); 75.54 (d); 74.75 (d); 70.78

(t, 2 PhCH₂); 70.62 (d, C(3)); 68.56 (t, C(8)); 0.42 (q, Me₃Si); 1s for CꢀC not observed or hidden. FAB-MS

(NOBA): 619 (56, [M 1] ), 497(100), 121(76). Anal. calc. for C₃₅H₄₂O₈Si (618.8): C 67.94, H 6.84; found:

C 67.75, H 6.89.

3,7-Anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol

(26). A soln. of 25 (128 mg, 0.21 mmol) in 80% aq. AcOH was stirred at r.t. for 90 min, evaporated, and co-

distilled (toluene). The resulting clear oil was dried under h.v. for 14 h to give 26 (103 mg, 99%). R_f(hexane/

AcOEt 4 :3) 0.15. [a]_D²⁵

43.0 (c 2, CHCl₃). IR (CCl₄): 3605m, 3455w (br.), 3001w, 2957m, 2935m, 2909m,

2836m, 2180w, 1741m, 1613m, 1586m, 1514s, 1464m, 1355m, 1302m, 1250s, 1180m, 1089s, 1040s, 846s. ¹H-NMR

(200 MHz, CDCl₃): 7.38 ± 7.24 (m, 4 arom. H); 6.94 ± 6.88 (m, 4 arom. H); 5.01 (d, J 10.4, ArCH); 4.91

(d, J 11.2, ArCH); 4.76 (d, J 10.2, ArCH); 4.64 (d, J 11.2, ArCH); 4.10 (d, J 9.6, H C(3)); 3.83

(s, MeO); 3.82 (s, MeO); 3.95 ± 3.70 (m, addn. of D₂O ! 3.87, dd, J 12.0, 3.3, H_aC(8), ! 3.73, dd, J 12.0,

5.0, H_bC(8)); 3.57 (t, J ꢁ 9.3, H C(5)); 3.52 (td, J ꢁ 8.9, 2.2, addn. of D₂O ! t, J ꢁ 9.0, H C(6)); 3.38 (t, J ꢁ

9.2, H C(4)); 3.29 (ddd, J 9.5, 5.0, 3.3, H C(7)); 2.44 (d, J 1.7, exchanged with D₂O, HO C(6)); 2.21

(br. t, J ꢁ 6.2, exchanged with D₂O, HO C(8)); 0.23 (s, Me₃Si). ¹³C-NMR (75 MHz, CDCl₃): 159.51 (s); 159.48

(s); 130.60 (s); 130.16 (s); 129.87 (2d); 129.59 (2d); 114.05 (2d); 113.85 (2d); 102.46 (s, CꢀCSi); 91.46

(s, CꢀCSi); 84.71 (d); 81.73 (d); 79.27 (d); 74.82 (d); 74.82 (t, ArCH₂); 70.09 (d, C(3)); 70.09 (t, ArCH₂); 62.34

(t, C(8)); 55.17 (q, MeO); 55.14 (q, MeO); 0.49 (q, Me₃Si). FAB-MS (NOBA): 499 (46, [M 1] ), 379 (95,

[M C₈H₉O] ), 361(8), 241(7), 137(11), 121(100), 73(7). Anal. calc. for C₂₇H₃₆O₇Si (500.66): C 64.77,

H 7.25; found: C 64.49, H 7.39.

3,7-Anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-gly-

cero-d-gulo-oct-1-ynitol (27). A soln. of 26 (400 mg, 0.8 mmol) and 1H-imidazole (136.2 mg, 2 mmol) in DMF

(2.5 ml) was treated at r.t. dropwise with thexyldimethylsilyl chloride (TDSCl; 0.19 ml, 0.96 mmol), stirred for

12 h, poured into ice-cold hexane/1m aq. HCl (1:1, 10 ml), and worked up (hexane). FC (hexane ! hexane/

Helvetica Chimica Acta ± Vol. 81 (1998)

2177

AcOEt 20 : 1 ! 10 : 1) gave 27 (494 mg, 95%). Colourles oil. R_f(hexane/AcOEt 4 : 3) 0.77. [a]_D²⁵

22.9 (c 1,

CHCl₃). IR (CCl₄): 3575m (br.), 3507m, 3001m, 2958s, 2909s, 2876s, 2836m, 2182w, 1878w, 1613s, 1586m,

1514s, 1464s, 1441m, 1394w, 1378w, 1354m, 1319m, 1301m, 1248s, 1216m, 1178m, 1173s, 1140s, 1089s, 1040s,

1012m, 908m, 845s. ¹H-NMR (400 MHz, CDCl₃): 7.31 ± 7.26 (m, 4 arom. H); 6.89 ± 6.85 (m, 4 arom. H); 4.92

(d, J 10.1, ArCH); 4.82 (d, J 11.0, ArCH); 4.79 (d, J 11.0, ArCH); 4.73 (d, J 10.1, ArCH); 4.02 (d, J

9.5, H C(3)); 3.90 (dd, J 10.5, 4.7, H_aC(8)); 3.80 (s, MeO); 3.79 (s, MeO); 3.79 (dd, J 10.5, 5.9,

H_bC(8)); 3.63 (td, J ꢁ 9.1, 2.2, addn. of D₂O ! t, J ꢁ 9.1, H C(6)); 3.50 (t, J ꢁ 9.3, H C(5)); 3.41 (t, J ꢁ 8.9,

H

C(4)); 3.27 (ddd, J 10.5, 5.9, 4.7, H C(7)); 3.05 (d, J 1.4, exchanged with D₂O, HO C(6)); 1.61

(sept., J 6.9, Me₂CH); 0.88 (br. d, J 6.9, Me₂CH); 0.85 (s, Me₂SiC); 0.19 (s, Me₃Si); 0.13 (s, MeSi); 0.12

(s, MeSi). ¹³C-NMR (100 MHz, CDCl₃): 159.36 (s); 159.26 (s); 130.96 (s); 130.35 (s); 129.84 (2d); 129.56 (2d);

113.88 (2d); 113.60 (2d); 102.62 (s, CꢀCSi); 91.03 (s, CꢀCSi); 84.92 (d, C(6)); 81.36 (d, C(5)); 78.02 (d, C(7));

75.00 (t, 2 ArCH₂); 73.41 (d, C(4)); 69.98 (d, C(3)); 64.68 (t, C(8)); 55.29 (q, MeO); 55.27 (q, MeO); 34.10

(d, Me₂CH); 25.22 (s, Me₂CSi); 20.33 (q, Me); 20.26 (q, Me); 18.50 (q, Me); 18.48 (q, Me); 0.27 (q, Me₃Si);

3.46 (q, MeSi); 3.47 (q, MeSi). FAB-MS (NOBA): 641 (22, [M 1] ), 521 (31, [M C₈H₉O] ), 281(6),

241(11), 207(10), 121(100), 73(12). Anal. calc. for C₃₅H₅₄O₇Si₂(642.98): C 65.38, H 8.46; found: C 65.32,

H 8.42.

2,3,6-Tri-O-acetyl-4-deoxy-4-C-ethynyl-a-d-glucopyranose (29). A soln. of 28 (300 mg, 0.84 mmol), in

DMF (2 ml), was treated in one batch with hydrazinium acetate (232 mg, 1.52 mmol), stirred for 5 h at 358,

poured into ice-cold 0.5m aq. HCl (10 ml) and worked up (Et₂O). Drying for 12 h at h.v. gave 29 (245.6 mg,

93%) as a colourless oil.

Data of a-d/b-d-29 (63 :37): R_f(hexane/AcOEt 1:1) 0.30. [a]²_D⁰ 57.2 (c 1.05, CHCl₃). IR (CHCl₃):

3595m, 3305s, 3040m, 2960w, 1745s, 1430w, 1370s, 1140m, 1045s, 935w, 905m, 655m, 605m. ¹H-NMR (200 MHz,

CDCl₃): 5.61 (t, J ꢁ 10.6, 0.63 H, H C(3)); 5.45 (t, J ꢁ 3.3, 0.63 H, H C(1)); 5.36 ± 5.24 (m, 0.37 H, H C(2));

4.79 (dd, J 10.1, 3.5, 0.63 H, H C(2)); 4.72 (t, J ꢁ 10.4, 0.37 H, H C(3)); 4.72 (dd, J 9.0, 6.0, 0.37 H,

H

C(1)); 4.52 ± 4.40 (m, H_aC(6)); 4.34 ± 4.25 (m, 1.63 H, H C(5), H_bC(6)); 3.76 (ddd, J 10.5, 5.3, 2.3,

0.37 H, H C(5)); 3.50 (br. d, J 5.9, 0.37 H, HO C(1)); 3.05 (br. d, J 2.9, 0.63 H, HO C(1)); 2.87 ± 2.72

(m, H C(4)); 2.17 (d, J 2.8, 0.37 H, H CꢀC); 2.16 (d, J 2.6, 0.63 H, H CꢀC); 2.12 (s, 2 Ac); 2.09 (s, Ac);

2.08 (s, Ac). ¹³C-NMR (50 MHz, CDCl₃): a-d-anomer: 171.26 (s, CO); 170.79 (s, CO); 170.28 (s, CO);

90.97 (d, C(1)); 78.43 (d, CꢀCH); 73.31 (s, CꢀCH); 71.90 (d); 69.25 (d); 68.67 (d); 64.19 (t); 36.11 (d); 20.97

(2q); 20.90 (q); b-d-anomer: 171.44 (s, CO); 95.87 (d, C(1)); 73.78 (s); 72.14 (2d); 64.67 (t); 36.20 (d); 21.23

(q); 20.81 (q). CI-MS: 332 (85, [M NH₄] ), 297 (65, [M OH] ), 272(48), 255(51), 195(100), 153(64),

135(50). Anal. calc. for C₁₄H₁₆O₈(314.29): C 53.50, H 5.77; found: C 53.49, H 5.77.

2,3,6-Tri-O-acetyl-4-deoxy-4-C-ethynyl-a-d-glucopyranosyl Trichloroacetimidate (30). A soln. of 29 (21.2 g,

67.9 mmol) and Cl₃CCN (40.8 ml, 0.407 mol) in CH₂Cl₂(600 ml) was treated in one batch with K₂CO₃(5.4 g),

stirred at r.t. for 48 h, filtered through Celite, concentrated to ca. 20 ml, and directly chromatographed (Æ 5 cm,

200 g of Si-60, hexane/AcOEt/Et₃N 2 :1:0.1). The product-containing fractions were concentrated to ca. 100 ml

and stored for 13 h at 208. Filtration gave 30/31 ca. 88 : 12 (22.6 g, 73%) as colourless needles. Evaporation of

the mother liquor gave additional 30/31 ca. 10 : 1 (3.2 g, 10%) as a white solid (total 25.8 g, 83%). Pure 30 was

obtained after recrystallization from hexane/AcOEt. R_f(hexane/AcOEt 1 : 1) 0.61. M.p. 135 ± 1368. [a]²_D⁵

89.8 (c 0.5, CHCl₃). IR (CCl₄): 3350w, 3311m, 2957w, 2110w, 1758s, 1676s, 1551w, 1430w, 1369s, 1293m, 1228s,

1148m, 1072s, 1024s, 971m, 948w, 914m, 900m, 834w. ¹H-NMR (200 MHz, CDCl₃): 8.65 (br. s, NH); 6.54 (d, J

3.6, H C(1)); 5.65 (t, J ꢁ 10.5, H C(3)); 5.01 (dd, J 10.0, 3.6, H C(2)); 4.43 (dd, J 12.1, 2.3, H_aC(6));

4.30 (dd, J 12.0, 4.3, H_bC(6)); 4.23 (ddd, J 10.8, 4.3, 2.3, H C(5)); 2.95 (td, J ꢁ 10.8, 2.4, H C(4)); 2.19

(d, J 2.3, H CꢀC); 2.11 (s, Ac); 2.10 (s, Ac); 2.01 (s, Ac). ¹³C-NMR (100 MHz, C₆D₆): 169.73 (s, CO);

169.53 (s, CO); 168.95 (s, CO); 161.11 (s, CN); 94.10 (d, C(1)); 91.10 (s, CCl₃); 78.04 (d, CꢀCH); 73.57

(s, CꢀCH); 71.86 (d); 70.85 (d); 69.32 (d); 63.70 (t, C(6)); 36.04 (d, C(4)); 20.28 (q, Me); 20.15 (q, Me); 19.90

(q, Me). CI-MS: 297 (100, [M aglycone] ), 254(28), 237(71), 195(66), 177(20), 166(11), 152(17), 134(23),

124(18), 60(12), 43(15). Anal. calc. for C₁₆H₁₈Cl₃NO₈(458.68): C 41.90, H 3.96, N 3.05; found: C 41.70, H 4.14,

N 2.97.

X-Ray Analysis of 30. Crystals were obtained by isothermic distillation of heptane into a ca. 10% soln. of 30

in AcOEt. C₁₆H₁₈Cl₃NO₈(458.68). Orthorhombic, P2₁2₁2₁, a 9.433(3) , b 10.516(3) , c 22.293(13) ,

V 2211(2) ³, Z 4, D_calc. 1.378 Mg/m³. The intensities were recorded on

a Enraf-Nonius-CAD-4

diffractometer (graphite monochromator, MoK_a, l 0.71073 ) at 293(2) K. Of the 2289 total collected

reflections, 2234 were independent. The structure was solved with direct methods (SHELXS96 [38]). The non-

H-atoms were refined anisotropically with SHELXL92 [35]. The H-atoms were calculated at idealised positions

and included in the structure factor calculation with fixed isotropic displacement parameters. Two of the three

2178

Helvetica Chimica Acta ± Vol. 81 (1998)

Cl-atoms and the 3-O- and 6-O-acyl groups were refined over two positions. The structure converged at an R

value of 0.0916 using 1578 reflections with I > 3s(I).

2,3,6-Tri-O-acetyl-4-deoxy-4-C-ethynyl-b-d-glucopyranosyl Trichloroacetimidate (31).

A soln. of 29

(586.2 mg, 1.87 mmol) and Cl₃CCN (1.87 ml, 18.65 mmol) in CH₂Cl₂(20 ml), was treated in one batch with

K₂CO₃(327 mg), stirred at r.t. for 90 min, filtered through Celite, concentrated to ca. 8 ml and directly

chromatographed (Æ 1 cm, 8 g of Si-60, hexane/AcOEt/Et₃N 2 :1 :0.1). The product-containing fractions were

concentrated to ca. 7 ml and stored for 4 h at 208. Filtration gave 31/30 ca. 83 : 17 (470 mg, 55%) as colourless

needles. Evaporation of the mother liquor gave additional 31/30 ca. 2 : 1 (128 mg 15%) as a white solid (total

598 mg, 70%). Pure 31 was obtained after recrystallization from heptane/ether. R_f(hexane/AcOEt 1 : 1) 0.61.

M.p. 174 ± 1758. [a]_D²⁵

6.9 (c 1, CHCl₃). IR (CCl₄): 3584w (br.), 3349w, 3311m, 2957w, 2111w, 1761s, 1677s,

1

1430w, 1367s, 1301m, 1227s, 1154m, 1125w, 1084s, 1060s, 948w, 898m, 837w. H-NMR (200 MHz, CDCl₃): 8.73

(br. s, NH); 5.87 (d, J 7.9, H C(1)); 5.36 (dd, J 10.8, 9.6, H C(3)); 5.16 (t, J 9.6, 8.3, H C(2)); 4.50

(dd, J 12.1, 2.5, H_aC(6)); 4.38 (dd, J 12.0, 4.6, H_bC(6)); 3.93 (ddd, J 10.6, 4.5, 2.5, H C(5)); 2.95

(td, J ꢁ 10.6, 2.4, H C(4)); 2.21 (d, J 2.3, H CꢀC); 2.13 (s, Ac); 2.12 (s, Ac); 2.04 (s, Ac). ¹³C-NMR

(75 MHz, CDCl₃): 170.72 (s, CO); 169.99 (s, CO); 169.41 (s, CO); 161.04 (s, CN); 95.80 (d, C(1)); 90.41

(s, CCl₃); 77.53 (d, CꢀCH); 73.73 (d); 73.51 (s, CꢀCH); 72.67 (d); 70.67 (d); 63.39 (t,C(6)); 35.23 (d, C(4));

20.65 (q, Me); 20.47 (q, Me); 20.44 (q, Me). CI-MS: 458 (2, M ), 297 (34, [M aglycone] ), 254(10), 237(38),

195(100), 177(35), 166(21), 153(16), 135(55), 124(28), 84(26), 43(45). Anal. calc. for C₁₆H₁₈Cl₃NO₈

(458.68): C 41.90, H 3.96, N 3.05; found: C 41.87, H 3.81, N 3.08.

X-Ray Analysis of 31. Crystals were obtained by isothermic distillation of pentane into a ca. 10% soln. of 31

in t-BuOMe. C₁₆H₁₈Cl₃NO₈(458.68). Monoclinic, P2₁, a 5.581(2) , b 8.891(3) , c 20.951(4) , b

94.39(3)8, V 1036.5(6) ³, Z 2, D_calc. 1.470 Mg/m³. The crystals were measured on an Enraf-Nonius-CAD-

4 diffractometer (graphite monochromator, CuK_a, l 1.54184 ) at 203(2) K. Of the 2178 total collected

reflections, 1983 were independent. An empirical absorption correction was done by PSI scans of selected

reflections. Part of the structure was solved with direct methods, the remaining non-H-atoms were found from a

difference Fourier map with SHELXS96 [38]. The non-H-atoms were refined anisotropically with SHELXL97

[39]. The H-atoms were refined isotropically except the H-atoms of the Me and alkyne groups, which were

calculated at idealized positions and included in the structure-factor calculation with fixed isotropic

displacement parameters. The disordered Cl-atoms were refined over two positions. The structure converged

at an R value of 0.0573 using 1867 reflections with I > 3s(I).

2,3,6-Tri-O-acetyl-4-deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-

methoxybenzyl)-8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (32). A soln. of 27

(6.69 g, 10.39 mmol) and 30 (5.23 g, 11.42 mmol) in CH₂Cl₂(100 ml) was treated with powdered 4- molecular

sieves (4 g) and stirred at r.t. for 30 min. The mixture was cooled to 108, treated dropwise with 1.41m Me₃SiOTf

in CH₂Cl₂(0.18 ml, 2.5 mol-%), stirred for 5 min, poured into ice-cold sat. NaHCO₃soln. (10 ml), filtered

through Celite, and worked up (CH₂Cl₂). FC (hexane/AcOEt 5 : 1 ! 7 : 2) gave 32 (8.8 g, 90%). Colourless oil.

R_f(hexane/AcOEt 2 : 1) 0.53. [a]_D²⁵

11.15 (c 2, CHCl₃). IR (CCl₄): 3311m, 2985s, 2902m, 2836m, 2183w,

1759s, 1613m, 1587w, 1514s, 1464m, 1441w, 1366m, 1294m, 1251s, 1231s, 1178m, 1089s, 1040s, 908m, 845s.

¹H-NMR (400 MHz, CDCl₃): 7.28 (dt, AA'BB', J_AB 8.9, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 7.20 (dt, AA'BB', J_AB

8.9, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 6.83 (dt, AA'BB', J_AB 8.9, J_AB'ꢁJ_AA'ꢁ2.0, 2 arom. H); 6.81 (dt, AA'BB', J_AB

8.9, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 5.19 ± 5.14 (m, M of ABMX, virtual coupling, J_MXꢁ 10.6, J_AMꢁ 9.2,

H

C(3')); 4.92 (d, J 10.9, ArCH); 4.82 ± 4.77 (m, H C(1'), H C(2'), ArCH); 4.65 (d, J 11.0, ArCH);

4.61 (d, J 11.0, ArCH); 4.33 (dd, J 12.1, 2.5, H_aC(6')); 4.28 (dd, J 12.1, 4.6, H_bC(6')); 3.91 (d, J 9.3,

H

C(3)); 3.89 ± 3.80 (m, 2 H C(8), H C(6)); 3.81 (s, MeO); 3.79 (s, MeO); 3.58 (ddd, J 10.4, 4.6, 2.5,

C(5')); 3.44 (t, J ꢁ 8.6, H C(5)); 3.40 (t, J ꢁ 8.7, H C(4)); 3.08 (br. ddd, J ꢁ 9.0, 2.4, 1.5, H C(7)); 2.81

(td, J ꢁ 10.5, 2.4, H C(4')); 2.13 (d, J 2.4, H C(8')); 2.06 (s, Ac); 2.03 (s, Ac); 2.00 (s, Ac); 1.66 (sept., J 6.9,

Me₂CH); 0.93 (d, J 6.9, MeCH); 0.92 (d, J 6.9, MeCH); 0.879 (s, MeCSi); 0.876 (s, MeCSi); 0.17 (s, Me₃Si);

0.16 (s, MeSi); 0.15 (s, MeSi). ¹³C-NMR (100 MHz, CDCl₃): 170.66 (s, CO); 169.96 (s, CO); 169.55

(s, CO); 159.26 (s); 158.97 (s); 131.46 (s); 130.45 (s); 129.80 (2d); 129.13 (2d); 113.68 (2d); 113.55 (2d); 102.94

(s, CꢀCSi); 99.98 (d, C(1')); 90.43 (s, CꢀCSi); 83.30 (d); 81.67 (d); 79.45 (d); 77.97 (d, HCꢀC); 76.36 (d); 75.16

(t, ArCH₂); 74.71 (t, ArCH₂); 73.13 (s, HCꢀC); 72.96 (d); 72.82 (d); 72.51 (d); 69.74 (d, C(3)); 63.95 (t, C(6'));

61.14 (t, C(8)); 55.27 (q, 2 MeO); 35.72 (d, C(4')); 34.27 (d, Me₂CH); 25.23 (s, Me₂CSi); 20.77 (q, Me); 20.73

(q, Me); 20.65 (q, Me); 20.53 (q, MeCH); 20.32 (q, MeCH); 18.76 (q, MeCSi); 18.60 (q, MeCSi); 0.30

(q, Me₃Si); 2.90 (q, MeSi); 3.21 (q, MeSi). FAB-MS (NOBA): 938 (60, [M 1] ), 817 (86, [M

C₈H₁₀O] ), 297 (8, [M aglycone] ), 241(6), 195(8), 121(100), 73(20, Me₃Si ). Anal. calc. for C₄₉H₇₀O₁₄Si₂

(939.25): C 62.66, H 7.51; found: C 62.86, H 7.62.

Helvetica Chimica Acta ± Vol. 81 (1998)

2179

4-Deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-

8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (33). soln. of 32 (12.3 g,

A

13.09 mmol) in THF (160 ml) was treated dropwise at 08 with 1.5m DIBAH in toluene (78.54 ml, 117.81 mmol),

stirred for 15 min, poured into ice/CHCl₃(1 : 1, 400 ml) and filtered through Celite. Workup (CHCl₃) and drying

for 12 h under h.v. gave 33 (10.5 g, 99%) as a colourless oil, which was used for the next step. An anal. sample

was purified by FC (hexane/AcOEt 1 : 2 ! 1 : 4). R_f(hexane/AcOEt 1 : 4) 0.36. [a]²_D⁵ 25.5 (c 2, CHCl₃). IR

(CCl₄): 3597m, 3442m (br.), 3310m, 2958s, 2905m, 2836m, 2182w, 1613s, 1586w, 1514s, 1464m, 1441w, 1353w,

1

1294m, 1282m, 1260s, 1180w, 1151m, 1080s, 1062s, 1039s, 913w, 845s. H-NMR (300 MHz, CDCl₃): 7.29 ± 7.21

(m, 4 arom. H); 6.89 ± 6.82 (m, 4 arom. H); 4.91 (d, J 10.0, ArCH); 4.82 (d, J 10.9, ArCH); 4.77 (d, J 10.9,

ArCH); 4.72 (d, J 10.0, ArCH); 4.65 (d, J 7.8, H C(1')); 3.97 (d, J 9.3, H C(3)); 3.91 (t, J ꢁ 9.5,

H

C(6)); 3.91 ± 3.84 (m, 2 H C(8)); 3.81 (s, MeO); 3.79 (s, MeO); 3.83 ± 3.78 (m, addn. of D₂O ! 3.80,

dd, J ꢁ 11.0, 2.5, H_aC(6')); 3.64 ± 3.50 (m, addn. of D₂O ! 3.62, dd, J 10.5, 5.6, H_bC(6')); 3.56 (t, J ꢁ 10.0,

H

C(3')); 3.51 (t, J ꢁ 9.0, H C(5)); 3.46 (t, J ꢁ 8.9, H C(4)); 3.34 (ddd, J 10.3, 5.6, 2.5, H C(5')); 3.25 ±

3.20 (m, HO C(2'), H C(7), addn. of D₂O ! 3.23, t, J ꢁ 9.0, H C(2')); 2.77 (br. s, exchanged with D₂O,

HO C(3')); 2.50 (td, J ꢁ 10.4, 2.4, H C(4')); 2.20 (d, J 2.4, H CꢀC); 1.99 (br. t, J ꢁ 0.8, exchanged with

D₂O, HO C(6')); 1.64 (sept., J 7.0, Me₂CH); 0.89 (d, J ꢁ 7.0, MeCH); 0.87 (d, J ꢁ 6.9, MeCH); 0.86

(s, 2 MeCSi); 0.19 (s, Me₃Si); 0.16 (s, MeSi); 0.14 (s, MeSi). ¹³C-NMR (75 MHz, CDCl₃): 159.41 (s); 159.28 (s);

130.74 (s); 130.29 (s); 129.82 (2d); 129.24 (2d); 113.76 (4d); 102.85 (s, CꢀCSi); 101.75 (d, C(1')); 90.61

(s, CꢀCSi); 83.67 (d); 81.76 (d); 80.21 (d, HCꢀC); 79.20 (d); 75.56 (d); 75.30 (d); 75.16 (d); 75.01 (d); 74.72

(t, 2ArCH₂); 72.78 (s, HCꢀC); 69.72 (d, C(3)); 62.81 (t, C(6')); 61.41 (t, C(8)); 55.13 (2q, MeO); 36.94

(d, C(4')); 33.97 (d, Me₂CH); 25.09 (s, Me₂CSi); 20.24 (q, MeCH); 20.10 (q, MeCH); 18.51 (q, MeCSi); 18.36

(q, MeCSi); 0.56 (q, Me₃Si); 3.11 (q, MeSi); 3.47 (q, MeSi). FAB-MS (NOBA): 811 (51, [M 2] ), 691

(37, [M C₈H₁₀O] ), 241(6), 121(100), 73 (21, Me₃Si ). Anal. calc. for C₄₃H₆₄O₁₁Si₂(813.14): C 63.52, H 7.93;

found: 63.06, H 8.16.

4-Deoxy-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-

(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (34). A soln. of

33 (1.26 mg, 1.55 mmol) and (Me₃Si)₂NH (1.07 ml, 5.12 mmol) in CH₂Cl₂(3 ml) was treated at r.t. with Me₃SiCl

(0.1 ml, 0.78 mmol), stirred for 30 min, poured into ice-water (10 ml) and worked up (hexane). The resulting

clear oil (1.6 g, R_f(hexane/AcOEt 4 : 1) 0.72) was dried for 8 h under h.v., dissolved in THF (15 ml), and

Me₃GeCl (0.3 ml, 2.3 mmol), cooled to 788, and treated dropwise with 1m LDA (freshly prepared from a soln.

of (i-Pr)₂NH (0.43 ml, 3 mmol) in THF (0.47 ml) and 1.43m BuLi in hexane (2.1 ml, 3 mmol) at 08) in THF/

hexane (1.9 ml), stirred for 5 min, poured into ice/sat. NH₄Cl soln. (1 : 1, 20 ml) and worked up (hexane). The

resulting clear oil (1.75 g, R_f(hexane/AcOEt 4 : 1) 0.74) was dissolved in H₂O/THF/AcOH 1 : 1 : 1 (30 ml),

stirred for 30 min at r.t., neutralized with sat. NaHCO₃soln., and worked up (CHCl₃). FC (hexane/AcOEt/

CH₂Cl₂6 : 1 : 1 ! 4 : 1 : 1) gave 34 (1.3 g, 90%). Colourless oil. R_f(hexane/AcOEt 9 : 11) 0.34. [a]²_D⁵ 30.6 (c

1, CHCl₃). IR (CCl₄): 3599m, 3431m (br.), 2958s, 2910m, 2876m, 2836m, 2122w, 1614m, 1586w, 1514s, 1464m,

1441w, 1365w, 1301m, 1251s, 1214w, 1172w, 1149m, 1089s, 1040s, 940w, 913w, 845s. ¹H-NMR (500 MHz, CDCl₃):

7.29 ± 7.22 (m, 4 arom. H); 6.87 (dt, AA'BB', J_AB 8.7, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 6.83 (dt, AA'BB', J_AB 8.7,

J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 4.90 (d, J 10.0, ArCH); 4.82 (d, J 10.6, ArCH); 4.74 (d, J 10.6, ArCH); 4.71

(d, J 10.0, ArCH); 4.63 (d, J 7.8, H C(1')); 3.97 (d, J 9.3, H C(3)); 3.98 ± 3.95 (m, H_aC(8)); 3.89 (t, J ꢁ

9.4, H C(6)); 3.91 ± 3.88 (m, H_bC(8)); 3.81 (s, MeO); 3.79 (s, MeO); 3.83 ± 3.78 (m, addn. of D₂O ! dd, J ꢁ

11.0, 2.7, H_aC(6')); 3.62 ± 3.50 (m, addn. of D₂O ! 3.58, dd, J 10.5, 6.3, H_bC(6'), ! 3.56 (t, J ꢁ 10.4,

H

C(3')); 3.50 (t, J ꢁ 8.9, H C(5)); 3.46 (t, J ꢁ 9.1, H C(4)); 3.33 (ddd, J 9.0, 6.3, 2.7, H C(5')); 3.25

(m, H C(2'), H C(6), addn. of D₂O ! 3.26, dd, J 9.0, 7.8, H C(2')); 3.23 (br. dt, J ꢁ 9.1, 2.2, H C(7)); 3.11

(d, J 2.1, exchanged with D₂O, HO C(2')); 2.61 (d, J 2.3, exchanged with D₂O, HO C(3')); 2.46 (t, J ꢁ

10.4, H C(4')); 2.07 (br. s, exchanged with D₂O, HO C(6')); 1.65 (sept., J 6.9, Me₂CH); 0.90 (d, J 6.8,

MeCH); 0.89 (d, J 6.9, MeCH); 0.865 (s, MeCSi); 0.862 (s, MeCSi); 0.33 (s, Me₃Ge); 0.19 (s, Me₃Si); 0.16

(s, MeSi); 0.14 (s, MeSi). ¹³C-NMR (75 MHz, CDCl₃): 159.25 (s); 159.12 (s); 130.81 (s); 130.27 (s); 129.66 (2d);

129.04 (2d); 113.61 (4d); 102.90 (s, CꢀCSi); 101.74 (d,C(1')); 100.46 (s, GeCꢀC); 90.33 (s, CꢀCSi); 89.34

(s, GeCꢀC); 83.46 (d); 81.81 (d); 79.10 (d); 75.63 (d); 75.51 (d); 74.96 (d); 74.90 (2t, ArCH₂); 74.62 (d); 69.57

(d, C(3)); 63.08 (t, C(6')); 61.29 (t, C(8)); 54.93 (2q, MeO); 38.35 (d, C(4')); 33.87 (d, Me₂CH); 24.96 (s, CSi);

20.15 (q, MeCH); 20.00 (q, MeCH); 18.40 (q, MeCSi); 18.27 (q, MeCSi); 0.35 (q, Me₃Ge); 0.44 (q, Me₃Si);

3.18 (q, MeSi); 3.57 (q, MeSi). FAB-MS (NOBA): 929 (10, M ), 241(31), 121(100), 119 (30, Me₃Ge ),

118(12), 117 (32, Me₃Ge ), 115(19), 73 (21, Me₃Si ). Anal. calc. for C₄₆H₇₂GeO₁₁Si₂(929.85): C 59.42, H 7.80;

found: C 59.55, H 7.56.

2180

Helvetica Chimica Acta ± Vol. 81 (1998)

4-Deoxy-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-

(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (35).

A soln. of 34 (1.2 g,

1.29 mmol) in THF (13 ml) was treated at r.t. with cold sat. K₂CO₃soln. in MeOH (1 ml), stirred for 1 h,

neutralized with Amberlite IR-120 (H form), filtered, and evaporated. FC (hexane/AcOEt/CH₂Cl₂5 : 1 : 1 !

4 : 1 : 1) gave 35 (1.01 g, 92%). Colourless oil. R_f(hexane/AcOEt 6 : 7) 0.42. [a]²_D⁵ 54.3 (c 1, CHCl₃). IR

(CCl₄): 3599m, 3466m (br.), 3311m, 2944m, 2900m, 2876m, 2836m, 2167w, 1741w, 1614m, 1586w, 1514s, 1465m,

1441w, 1355w, 1301m, 1249s, 1172w, 1150m, 1091s, 1040s, 938w, 832s. ¹H-NMR (500 MHz, CDCl₃): 7.29

(dt, AA'BB', J_ABꢁ 8.8, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 7.26 (dt, AA'BB', J_ABꢁ 8.6, J_AB'ꢁ J_AA'ꢁ 2.1, 2 arom. H); 6.87

(dt, AA'BB', J_AB 8.9, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 6.84 (dt, AA'BB', J_AB 8.9, J_AB'ꢁ J_AA'ꢁ 2.0, 2 arom. H); 4.88

(d, J 10.0, ArCH); 4.83 (d, J 10.6, ArCH); 4.75 (d, J 10.6, ArCH); 4.74 (d, J 10.0, ArCH); 4.64 (d, J

7.8, H C(1')); 4.02 ± 3.97 (m, addn. of D₂O ! 3.99, dd, J 12, 2.7, H_aC(6'), ! 3.98, dd, J 9.3, 2.1, H C(3));

3.92 ± 3.88 (m, H_aC(8)); 3.90 (t, J ꢁ 9.2, H C(6)); 3.80 ± 3.76 (m, addn. of D₂O ! signal changed, H_bC(6'));

3.80 (s, MeO); 3.79 (s, MeO); 3.82 ± 2.79 (m, addn. of D₂O ! signal changed, H_aC(6')); 3.58 ± 3.52 (m, addn.

of D₂O ! 3.55, dd, J 10.4, 9.0, H C(3'), ! 3.53, dd, J ꢁ 11.0, 2.2, H_bC(8)); 3.52 (t, J ꢁ 8.9, H C(5)); 3.47

(t, J ꢁ 9.2, H C(4)); 3.33 (ddd, J 10.0, 6.0, 2.8, H C(5')); 3.30 ± 3.25 (m, addn. of D₂O ! 3.27, dd, J ꢁ 9.0, 7.8,

H

C(2'), ! 3.25, br. dt, J ꢁ 9.1, 2.0, H C(7)); 3.06 (d, J 2.0, exchanged with D₂O, HO C(2')); 2.61 (d, J

2.3, exchanged with D₂O, HO C(3')); 2.49 (d, J 2.1, H C(1)); 2.48 (td, J ꢁ 10.3, 2.4, H C(4')); 1.98

(br. t, J ꢁ 7.5, exchanged with D₂O, HO C(6')); 1.65 (sept., J 6.9, Me₂CH); 0.90 (d, J 6.8, MeCH); 0.89

(d, J 6.9, MeCH); 0.86 (s, Me₂CSi); 0.33 (s, Me₃Ge); 0.15 (s, MeSi); 0.14 (s, MeSi). ¹³C-NMR (100 MHz,

CDCl₃): 159.39 (s); 159.17 (s); 130.91 (s); 130.22 (s); 129.85 (2d); 128.96 (2d); 113.38 (2d); 113.79 (2d); 101.96

(d, C(1')); 100.02 (s, GeCꢀC); 90.05 (s, GeCꢀC); 83.92 (d); 81.82 (d); 81.07 (d, C(1)); 79.53 (d); 75.72 (2d);

75.28 (t, ArCH₂); 75.16 (t, ArCH₂); 75.06 (d); 74.95 (d); 73.65 (s, C(2)); 69.44 (d, C(3)); 63.38 (t, C(6')); 61.60

(t, C(8)); 55.31 (q, MeO); 55.30 (q, MeO); 38.61 (d, C(4')); 34.12 (d, Me₂CH); 25.28 (s, Me₂CSi); 20.45

(q, MeCH); 20.25 (q, MeCH); 18.71 (q, MeCSi); 18.54 (q, MeCSi); 0.11 (q, Me₃Ge); 2.82 (q, MeSi); 3.27

(q, MeSi). FAB-MS (NOBA): 857 (52, M ), 855(35), 737(31), 569(6), 121(100), 119 (13, Me₃Ge ), 117(10),

73 (16, Me₃Si ). Anal. calc. for C₄₃H₆₄GeO₁₁Si (857.67): C 60.22, H 7.52; found: C 60.05, H 7.27.

2,3,6-Tri-O-acetyl-4-C-(bromoethynyl)-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-

bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (36). A

soln. of 34 (156mg, 0.167 mmol) in CH₂Cl₂(1 ml), pyridine (0.2 ml), and Ac₂O (0.15 ml) was stirrd for 12 h,

evaporated, co-distilled (toluene), and dried under h.v. for 12 h. The resulting slightly yellow oil (R_f(hexane/

AcOEt 2 : 1) 0.60) and NBS (44.6 mg, 0.25 mmol) were dissolved in acetone (1.6 ml), treated with CuBr

(4.8 mg, 20 mol-%), stirred at r.t. for 2 h, poured into ice-cold 10% aq. Na₂S₂O₃soln. (4 ml), and worked up

(Et₂O). FC (hexane/AcOEt 6 : 1) gave 36 (152.8 mg, 90%). Colourless oil. R_f(hexane/AcOEt 6 : 7) 0.85.

[a]²_D⁵

2.5 (c 1, CHCl₃). IR (CCl₄): 2960s, 2902m, 2836m, 2183w, 1759s, 1613m, 1587w, 1514s, 1464m, 1441w,

1366m, 1301m, 1251s, 1230s, 1173m, 1089s, 1055s, 1040s, 901m, 845s. ¹H-NMR (400 MHz, CDCl₃): 7.28 ± 7.19

(m, 4 arom. H); 6.83 ± 6.79 (m, 4 arom. H); 5.20 ± 5.10 (m, M of ABMX, virtual coupling, J_MXꢁ 10.2, J_AMꢁ 9.1,

H

C(3')); 4.89 (d, J 10.8, ArCH); 4.84 ± 4.72 (m, H C(1'), H C(2'), ArCH); 4.64 (d, J 11.0, 2 ArCH);

4.61 (d, J 10.8, ArCH); 4.32 (dd, J 11.5, 2.9, H_aC(6')); 4.23 (dd, J 11.5, 4.5, H_bC(6')); 3.92 (d, J 9.1,

C(3)); 3.86 ± 3.76 (m, H_aC(8), H_bC(8), H C(6)); 3.81 (s, MeO); 3.79 (s, MeO); 3.59 (ddd, J 10.0, 4.6,

H

2.9, H C(5')); 3.44 (t, J ꢁ 8.7, H C(5)); 3.39 (t, J ꢁ 9.1, H C(4)); 3.08 (br. d, J ꢁ 10.0, H C(7)); 2.82 (t, J ꢁ

10.4, H C(4')); 2.07 (s, Ac); 2.03 (s, Ac); 2.01 (s, Ac); 1.67 (sept., J 7.0, Me₂CH); 0.93 (d, J 7.0, MeCH);

0.92 (d, J 7.0, MeCH); 0.88 (s, Me₂CSi); 0.17 (s, Me₃Si); 0.16 (s, 2 MeSi). ¹³C-NMR (75 MHz, CDCl₃): 170.72

(s, CO); 169.93 (s, CO); 169.62 (s, CO); 159.37 (s); 159.09 (s); 131.49 (s); 130.50 (s); 129.84 (2d); 129.16

(2d); 113.69 (2d); 113.58 (2d); 102.95 (s, CꢀCSi); 99.94 (d, C(1')); 90.38 (s, CꢀCSi); 83.23 (d); 81.64 (d); 79.39

(d); 76.30 (d); 75.08 (t, ArCH₂); 74.64 (t, ArCH₂); 74.04 (s, BrCꢀC); 72.75 (d); 72.49 (2d); 69.67 (d, C(3));

63.98 (t, C(6')); 61.05 (t, C(8)); 55.16 (q, 2 MeO); 44.27 (s, BrCꢀC); 36.88 (d, C(4')); 34.15 (d, Me₂CH); 25.10

(s, Me₂CSi); 20.59 (q, Me); 20.47 (q, Me); 20.39 (q, Me); 20.18 (q, Me₂CH); 18.60 (q, MeCSi); 18.44

(q, MeCSi); 0.51 (q, Me₃Si); 3.13 (q, MeSi); 3.39 (q, MeSi). FAB-MS (NOBA): 1017 (30, [M(⁸¹Br)

1] ), 1015 (24, [M(⁷⁹Br) 1] ), 897(46), 895(40), 377 (8, [M(⁸¹Br) aglycone] ), 375 (8, [M(⁷⁹Br)

aglycone] ), 199(13), 197(13), 121(100), 73 (19, Me₃Si ). Anal. calc. for C₄₉H₆₉BrO₁₄Si₂(1018.16): C 57.80,

H 6.83; found: C 57.73, H 6.53.

4-Deoxy-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-

bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-

tri-O-acetyl-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-

(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (37) and 4-Deoxy-4-C-{4-[2,3,6-tri-O-

acetyl-b-d-glucopyranose-1,4-diyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O(thexyl-

Helvetica Chimica Acta ± Vol. 81 (1998)

2181

dimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol-6-yl]buta-1,3-diyne-1-yl}-b-d-glucopyranosyl-

(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-

gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-

dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-

ynitol (38). A degassed soln. of 35 (432 mg, 0.504mmol), 36 (513 mg, 0.504mmol), [Pd₂(dba)₃] (13.8 mg,

3 mol-%), CuI (2.9 mg, 3 mol-%), and P(furyl)₃(7.0 mg, 6 mol-%) in DMSO (5 ml) was treated at r.t. with

Et₃N (0.3 ml), stirred at r.t. for 6 h, poured into ice-cold sat. NH₄Cl soln. (5 ml), and worked up (CH₂Cl₂). FC

(hexane/CH₂Cl₂/AcOEt 1 : 1 : 0 ! 3 : 1 : 1 ! 2 : 1 : 1 ! 4 : 2 : 3) gave 36 (39.5 mg, 8%), 37 (586 mg, 65%), and 35

(18.6 mg, 4%) as colourless oils.

In an analogous experiment, the reaction time was extended to 17 h, and additionally 38 (2%) was isolated

as a colourless oil.

Data of 37: R_f(hexane/AcOEt 6 :7) 0.40. [a]_D²⁵

3.4 (c 1.2, CHCl₃). IR (CCl₄): 3599m, 3457m (br.),

2958s, 2908m, 2875m, 2836m, 2170w, 1759s, 1613m, 1587m, 1514s, 1464m, 1441m, 1366m, 1302m, 1250s, 1230s,

1172m, 1151m, 1089s, 1040s, 946w, 913w, 832s. ¹H-NMR (500 MHz, CDCl₃, assignment based on H,H-COSY):

7.28 ± 7.19 (m, 8 arom. H); 6.88 ± 6.80 (m, 8 arom. H); 5.18 ± 5.12 (m, M of ABMX, virtual coupling, J_MXꢁ 10.6,

J_AMꢁ 9.3, irrad. at 2.92 ppm ! ABM, m, virtual coupling, J_AMꢁ 9.3, irrad. at 4.99 ! d, J_MX 10.6, H C(3'));

4.89 (d, J 11.0, ArCH); 4.83 (d, J 10.6, ArCH); 4.82 ± 4.78 (m, AB of H C(1')/H C(2'), 2 ArCH); 4.74

(d, J 10.6, ArCH); 4.72 (d, J 10.8, ArCH); 4.64 (d, J 10.8, ArCH); 4.62 (d, J 7.8, H C(1''')); 4.60 (d, J

10.9, ArCH); 4.31 (dd, J 11.8, 2.7, H_aC(6')); 4.24 (dd, J 11.8, 4.7, H_bC(6')); 4.00 (d, J 9.5, H C(3));

3.96 (dd, J 9.0, 2.8, H_aC(8)); 3.90 (d, J 9.3,

H

C(5'')); 3.88 (t, J ꢁ 10.0,

H C(6)); 3.86 ± 3.83

(m, H_aC(10''), H_bC(8)); 3.85 (t, J ꢁ 9.2, H C(8'')); 3.81 (s, MeO); 3.80 (s, 2 MeO); 3.78 (s, MeO); 3.79 ±

3.76 (m, addn. of D₂O, signal changed, H_aC(6'''), H_bC(10'')); 3.59 (ddd, J 10.3, 4.6, 2.7, H C(5')); 3.57 ±

3.50 (m, addn. of D₂O ! 3.55, dd, J 10.2, 9.1, H C(3'''), ! 3.52, dd, J 10.9, 6.2, H_bC(6'''), ! 3.50, t, J ꢁ 9.0,

H

C(5)); 3.43 (t, J ꢁ 9.3, H C(4)); 3.42 (t, J ꢁ 8.9, H C(7'')); 3.39 (t, J ꢁ 9.0, H C(6'')); 3.35 ± 3.33 (m, addn.

of D₂O ! 3.35, ddd, J 10.2, 6.2, 2.6, H C(5''')); 3.26 (br. t, addn. of D₂O ! t, J ꢁ 8.4, H C(2''')); 3.22

(br. dt, J ꢁ 9.6, 1.8, H C(7)); 3.09 ± 3.07 (m, addn. of D₂O ! 3.09, br. ddd, J ꢁ 9.7, 2.8, 1.5, H C(9'')); 3.04

(d, J 2.1, exchanged with D₂O, HO C(2''')); 2.93 (t, J ꢁ 10.3, H C(4')); 2.66 (d, J 2.2, exchanged with D₂O,

HO C(3''')); 2.47 (t, J ꢁ 10.4, H C(4''')); 2.02 (s, Ac); 2.01 (s, Ac); 1.98 (s, Ac); 1.70 ± 1.60 (m, HO C(6'''),

addn. of D₂O ! 1.64, sept., J 6.9, Me₂CH, ! 1.63, sept., J 6.9, Me₂CH); 0.92 (d, J 6.9, MeCH); 0.91 (d, J

6.9, MeCH); 0.90 (d, J 6.9, MeCH); 0.89 (d, J 6.9, MeCH); 0.869 (s, MeCSi); 0.866 (s, MeCSi); 0.857

(2s, MeCSi); 0.33 (s, Me₃Ge); 0.17 (s, Me₃Si); 0.152 (s, MeSi); 0.147 (s, MeSi); 0.143 (s, MeSi); 0.134 (s, MeSi).

¹³C-NMR (125 MHz, CDCl₃): 170.45 (s, CO); 169.64 (s, CO); 169.51 (s, CO); 159.46 (s); 159.26 (s);

159.22 (s); 158.99 (s); 131.38 (s); 130.81 (s); 130.38 (s); 1 arom. s not observed or hidden; 129.92 (2d); 129.78

(2d); 129.12 (2d); 128.96 (2d); 113.92 (2d); 113.79 (2d); 113.68 (2d); 113.57 (2d); 102.92 (s, CꢀCSi); 101.92

(d, C(1''')); 100.01 (s, CꢀCGe); 99.94 (d, C(1')); 90.43 (s, CꢀCSi); 90.07 (s, CꢀCGe); 83.85 (d); 83.22 (d); 81.68

(d); 81.45 (d); 79.75 (d); 79.43 (d); 76.39 (d); 75.73 (d); 75.66 (d); 75.32 (t, ArCH₂); 75.26 (s, C(1'')); 75.17

(t, ArCH₂); 75.14 (t, ArCH₂); 75.09 (d); 74.91 (d); 74.71 (t, ArCH₂); 73.87 (s, C(4'')); 72.57 (d); 72.46 (d); 72.41

(d); 70.01 (d, C(5'')); 69.74 (d, C(3)); 69.42 (s, C(3'')); 68.77 (s, C(2'')); 64.02 (t); 63.36 (t); 61.52 (t); 61.13 (t);

55.31 (q, MeO); 55.27 (q, 2 MeO); 55.25 (q, MeO); 38.63 (d, C(4''')); 36.78 (d, C(4')); 34.26 (d, Me₂CH); 34.21

(d, Me₂CH); 25.28 (s, Me₂CSi); 25.23 (s, Me₂CSi); 20.74 (q, Me); 20.67 (q, Me); 20.54 (q, Me); 20.46

(q, MeCH); 20.34 (q, MeCH); 20.32 (q, MeCH); 20.23 (q, MeCH); 18.75 (q, MeCSi); 18.70 (q, MeCSi);

18.59 (q, MeCSi); 18.52 (q, MeCSi); 0.12 (q, Me₃Ge); 0.31 (q, Me₃Si); 2.85 (q, MeSi); 2.90 (q, MeSi);

3.18 (q, MeSi); 3.24 (q, MeSi). MALDI-TOF-MS: 1834 ([M K] ), 1818 ([M Na] ). Anal. calc. for

C₉₂H₁₃₂GeO₂₅Si₃(1794.91): C 61.56, H 7.41; found: C 61.76, H 7.40.

Data of 38: R_f(hexane/AcOEt 6 :9) 0.37. [a]_D²⁵ 6.7 (c 1.2, CHCl₃). IR (CCl₄): 3596m, 3460m (br.),

2959s, 2907m, 2876m, 2836m, 2172w, 1759s, 1613m, 1587m, 1515s, 1464m, 1441m, 1365m, 1302m, 1251s, 1229s,

1172m, 1151m, 1089s, 1041s, 946w. ¹H-NMR (500 MHz, CDCl₃): 7.28 ± 7.15 (m, 12 arom. H); 6.88 ± 6.77

(m, 12 arom. H); 5.18 ± 5.13 (m,M of ABMX, virtual coupling, J_MXꢁ 10.5, J_AMꢁ 9.4, H C(3')); 5.12 ± 5.08

(m, M of ABMX, virtual coupling, J_MXꢁ 10.6, J_AMꢁ 9.3, H C(3^IV)); 4.89 (d, J 11.3, ArCH); 4.88 (d, J 11.2,

ArCH); 4.82 ± 4.67 (m, H C(1'), H C(2'), H C(1^IV), H C(2^IV), 8 ArCH); 4.64 (d, J 10.5, ArCH); 4.63

(d, J 7.8, H C(1''')); 4.61 (d, J 11.2, ArCH); 4.32 (br. dd, J ꢁ 11.5, 2.3, H_aC(6'), H_aC(6^IV)); 4.24 (dd, J

12.0, 4.9, H_bC(6')); 4.23 (dd, J 12.0, 5.0, H_bC(6^IV)); 4.01 (br. d, J ꢁ 9.5, H C(3), H C(3^V)); 3.96

(br. dd, J ꢁ 11.5, 2.5, H_aC(8)); 3.95 (dd, J ꢁ 11.5, 2.2, H_aC(8^V)); 3.91 (d, J 9.3, H C(5'')); 3.89 ± 3.72

(m, addn. of D₂O ! signal changed, H_bC(8), H_bC(8^V), H_aC(10''), H C(6), H C(8''), H C(6^IV)); 3.809

(s, MeO); 3.806 (s, MeO); 3.80 (s, MeO); 3.79 (s, MeO); 3.78 (s, 2 MeO); 3.76 ± 3.64 (m, addn. of D₂O ! signal

changed, H_bC(10''), H_aC(6''')); 3.62 ± 3.53 (m, addn. of D₂O ! 3.59, ddd, J 11.5, 4.7, 2.5, H C(5'), ! 3.58,

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Helvetica Chimica Acta ± Vol. 81 (1998)

dd, J 10.5, 9.1, H C(3'''), ! 3.55, ddd, J ꢁ 10.0, 4.9, 2.8, H C(5^IV)); 3.52 ± 3.46 (m, addn. of D₂O ! 3.49,

dd, J 11.0, 5.5, H_bC(6'''), ! 3.48 t, J ꢁ 9.1, H C(5), ! 3.47, t, J ꢁ 9.2, H C(5^V)); 3.43 (t, J ꢁ 9.4, H C(4));

3.42 (t, J ꢁ 9.0, H C(7'')); 3.41 (t, J ꢁ 8.9, H C(4^V)); 3.39 (t, J ꢁ 8.7, H C(6'')); 3.12 (br. ddd, addn. of D₂O !

ddd, J 10.2, 5.4, 2.1, H C(5''')); 3.25 ± 3.19 (m, addn. of D₂O ! 3.22, dd, J 9.1, 7.8, H C(2'''), additionally

H

C(7),

H

C(7^V)); 3.16 (br. d, J ꢁ 2.1, exchanged with D₂O, HO C(2''')); 3.08 (br. dt, J ꢁ 8.8, 1.3,

C(9'')); 2.93 (t, J ꢁ 10.5, H C(4')); 2.89 (t, J ꢁ 10.4, H C(4^IV)); 2.71 (d, J 2.9, exchanged with D₂O,

HO C(3''')); 2.58 (br. td, addn. of D₂O ! t, J ꢁ 10.5, H C(4''')); 2.07 (s, Ac); 2.019 (s, Ac); 2.018 (s, Ac); 2.01

(s, Ac); 1.99 (s, Ac); 1.98 (s, Ac); 1.81 (br. s, exchanged with D₂O, HO C(6''')); 1.65 (sept., J ꢁ 6.9, 2 Me₂CH);

1.64 (sept., J 6.9, Me₂CH); 0.94 (d, J 6.9, MeCH); 0.93 (d, J 6.9, MeCH); 0.92 (d, J 6.9, MeCH); 0.91

(d, J 6.9, MeCH); 0.89 (d, J 6.9, MeCH); 0.88 (d, J 6.9, MeCH); 0.88 (s, MeCSi); 0.879 (s, MeCSi); 0.868

(s, MeCSi); 0.865 (s, MeCSi); 0.855 (s, 2 MeCSi); 0.173 (s, Me₃Si); 0.172 (s, Me₃Si); 0.16 (s, MeSi); 0.15

(s, 2 MeSi); 0.146 (s, 2 MeSi); 0.14 (s, MeSi). ¹³C-NMR (125 MHz, CDCl₃): 170.59 (s, CO); 170.45 (s, CO);

169.80 (s, CO); 169.64 (s, CO); 169.52 (s, CO); 169.50 (s, CO); 159.49 (s); 159.27 (2s); 159.24 (s); 158.99

(s); 158.98 (s); 131.43 (s); 131.39 (s); 130.75 (s); 130.44 (2s); 129.94 (2d); 129.88 (s); 129.79 (4d); 129.11 (2d);

129.07 (2d); 128.75 (2d); 113.93 (2d); 113.84 (2d); 113.68 (4d); 113.57 (4d); 102.94 (s, CꢀCSi); 102.92

(s, CꢀCSi); 101.99 (d, C(1''')); 99.95 (d, C(1')); 99.90 (d, C(1^IV)); 90.44 (s, CꢀCSi); 90.42 (s, CꢀCSi); 83.98 (d);

83.28 (d); 83.23 (d); 81.68 (2d); 81.47 (d); 79.60 (d); 79.43 (2d); 76.40 (d); 76.37 (d); 75.65 (d); 75.33

(t, 2 ArCH₂); 75.15 (t, 2 ArCH₂); 75.15 (d); 75.08 (d); 74.72 (t, 2 ArCH₂); 74.36 (d); 73.95 (s); 72.58 (d); 72.56

(d); 72.53 (2d); 72.45 (d); 72.41 (d); 72.05 (s); 70.04 (d); 69.74 (2d); 69.49 (s); 69.06 (s); 68.74 (s); 68.55 (s);

67.93 (s); 64.05 (t); 64.02 (t); 63.01 (t); 61.57 (t); 61.14 (t); 61.11 (t); 55.33 (q, 3 MeO); 55.27 (q, 3 MeO); 37.53

(d); 36.78 (d); 36.50 (d); 34.28 (d, 2 MeCH); 34.08 (d, MeCH); 25.32 (s, MeCSi); 25.25 (s, MeCSi); 25.24

(s, MeCSi); 20.75 (q, 2 Me); 20.71 (q, Me); 20.67 (q, Me); 20.56 (q, Me); 20.54 (q, Me); 20.52 (q, Me); 20.47

(q, Me); 20.35 (q, 2 Me); 20.34 (q, Me); 20.25 (q, Me); 18.78 (q, Me); 18.75 (q, Me); 18.71 (q, Me); 18.61

(q, Me); 18.60 (q, Me); 18.52 (q, Me); 0.30 (q, Me₃Si); 2.88 (q, MeSi); 2.90 (q, MeSi); 2.92 to 3.18

(q, 2 MeSi); 3.20 (q, MeSi); 1s for CꢀC not observed or hidden. MALDI-TOF-MS: 2639 ([M Na] ). Anal.

calc. for C₁₃₈H₁₉₃O₃₉Si₅´ AcOEt (2692.58): C 62.69, H 7.45; found: 62.40, H 7.27.

4-Deoxy-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-

bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-

b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-

d-glycero-d-gulo-oct-1-ynitol (39). A soln. of 37 (721 mg, 0.4 mmol) in THF (10 ml) was treated dropwise at 08

with cold sat. K₂CO₃soln. in MeOH (0.5 ml), stirred for 6 h, neutralized with Amberlite IR-120 (H form),

filtered, and evaporated. FC (CHCl₃! CHCl₃/MeOH 20 : 1) gave 39 (497 mg, 78%). Colourless oil. R_f(CHCl₃/

MeOH 20 : 1) 0.31. [a]²_D⁵ 21.8 (c 1.1, CHCl₃). IR (CCl₄): 3593m, 3481m (br.), 3312m, 2957m, 2878m,

2836m, 2169w, 1613m, 1586w, 1558w, 1514s, 1464m, 1441w, 1356w, 1301m, 1273w, 1250s, 1172m, 1150m, 1090s,

1061s, 1040s, 910w, 874w, 832s. ¹H-NMR (500 MHz, CDCl₃): 7.30 ± 7.21 (m, 8 arom. H); 6.88 ± 6.80 (m, 8

arom. H); 4.88 (d, J 10.0, ArCH); 4.84 (d, J 10.6, ArCH); 4.81 (d, J 10.6, ArCH); 4.80 (d, J 10.5,

ArCH); 4.76 (d, J 11.9, 2 ArCH); 4.74 (d, J 11.8, ArCH); 4.73 (d, J 10.1, ArCH); 4.65 (d, J 8.3,

H

C(1''')); 4.63 (d, J 7.7, H C(1')); 4.04 ± 3.93 (m, addn. of D₂O ! 4.02, d, J 9.5, H C(5''), ! 3.98, dd, J

9.4, 2.1, H C(3), ! 3.97, dd, J ꢁ 11.0, 2.4, H_aC(6'), ! 3.95, dd, J ꢁ 11.0, 4.0, H_aC(6''')); 3.91 (t, J ꢁ 9.6,

H

C(6)); 3.88 (t, J ꢁ 9.5,

H

C(8'')); 3.88 (br. dd, J ꢁ 12.0, 2.0, H_aC(8)); 3.86 (br. dd, J ꢁ 12.0, 1.5,

H_aC(10'')); 3.81 (s, MeO); 3.79 (s, MeO); 3.786 (s, MeO); 3.784 (s, MeO); 3.81 ± 3.75 (m, addn. of D₂O !

signal changed, H_bC(6'), H_bC(6''')); 3.60 ± 3.50 (m, H_bC(8), H_bC(10''), addn. of D₂O ! 3.61, dd, J

10.4, 9.0, H C(3'), ! 3.56, dd, J 10.3, 9.0, H C(3'''), ! 3.52, t, J ꢁ 9.0, H C(7''), ! 3.51, t, J ꢁ 9.0, H C(5));

3.47 (t, J ꢁ 9.3, H C(4)); 3.43 (t, J ꢁ 9.4, H C(6'')); 3.38 ± 3.31 (m, addn. of D₂O ! signal changed, H C(5'),

H

C(5''')); 3.26 ± 3.23 (m, addn. of D₂O ! signal changed, H C(7'), H C(9''), HO C(3'), ! 3.26, dd, J

9.0, 7.8, H C(2'), ! 3.25, t, J ꢁ 8.8, H C(2''')); 3.25 (br. s, exchanged with D₂O, HO C(2')); 3.08 (br. s,

exchanged with D₂O, HO C(2''')); 2.66 (t, J ꢁ 10.4, H C(4')); 2.63 (br. s, exchanged with D₂O, HO C(3'''));

2.50 (d, J 2.1, H C(1)); 2.48 (t, J ꢁ 10.3, H C(4''')); 2.01 (br. t, J ꢁ 6.0, addn. of D₂O, HO C(6')); 1.93

(br. t, J ꢁ 6.5, addn. of D₂O, HO C(6''')); 1.65 (sept., J 6.9, Me₂CH); 1.64 (sept., J 6.9, Me₂CH); 0.90 (d, J

6.9, MeCH); 0.89 (d, J 6.9, MeCH); 0.883 (d, J 6.9, MeCH); 0.875 (d, J 6.9, MeCH); 0.86 (s, 2 MeCSi);

0.85 (s, 2 MeCSi); 0.33 (s, Me₃Ge); 0.150 (s, MeSi); 0.145 (s, MeSi); 0.14 (s, 2 MeSi). ¹³C-NMR (100 MHz,

CDCl₃): 159.41 (2s); 159.23 (s); 159.22 (s); 130.18 (2s); 130.03 (2s); 129.99 (2d); 129.86 (2d); 128.99 (2d);

128.83 (2d); 113.93 (2d); 113.84 (2d); 113.83 (2d); 113.81 (2d); 101.99 (d, C(1''')); 101.94 (d, C(1')); 100.03

(s, CꢀCGe); 90.06 (s, CꢀCGe); 84.02 (d); 83.98 (d); 81.82 (d); 81.51 (d); 81.01 (d, CꢀCH); 79.69 (d); 79.40 (d);

76.20 (s); 75.72 (d); 75.68 (d); 75.65 (d); 75.34 (t, ArCH₂); 75.34 (d); 75.27 (t, ArCH₂); 75.18 (t, ArCH₂); 75.13

(t, ArCH₂); 75.13 (d); 75.09 (d); 74.91 (d); 74.75 (s, CꢀCH); 74.47 (d); 73.75 (s); 70.04 (d, C(5'')); 69.76 (s);

Helvetica Chimica Acta ± Vol. 81 (1998)

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69.47 (d, C(3)); 69.52 (s); 63.36 (t); 63.02 (t); 61.63 (t); 61.51 (t); 55.31 (q, 4 MeO); 38.62 (d, C(4''')); 37.66

(d, C(4')); 34.21 (d, MeCH); 34.10 (d, MeCH); 25.30 (s, MeCSi); 25.28 (s, MeCSi); 20.47 (q, 2 MeCH); 20.46

(q, MeCH); 20.24 (q, MeCH); 18.72 (q, MeCSi); 18.71 (q, MeCSi); 18.53 (q, 2 MeCSi); 0.11 (q, Me₃Ge);

2.79 (q, MeSi); 2.83 (q, MeSi); 3.24 (q, MeSi); 3.26 (q, MeSi). MALDI-TOF-MS: 1620 ([M Na] ).

Anal. calc. for C₈₃H₁₁₈GeO₂₂Si₂´ CH₃OH (1628.65): C 61.96, H 7.55; found: C 61.79, H 7.35.

4-C-(Bromoethynyl)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-

methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-

4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldi-

methylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (40). A soln. of 37 (550 mg, 0.306 mmol) and

NBS (65.4 mg, 0.37 mmol) in acetone (3 ml) was treated with CuBr (13.19 mg, 30 mol-%), stirred for 1 h,

poured into ice-cold sat. Na₂S₂O₃soln. (5 ml), and worked up (CH₂Cl₂). FC (hexane/CH₂Cl₂/AcOEt 1 : 1 : 1 !

4 : 2 : 3) gave 40 (441 mg, 81%). Amorphous solid. R_f(hexane/AcOEt 6 : 7) 0.40. [a]_D²⁵

2.6 (c 1.1, CHCl₃).

IR (CCl₄): 3589m, 3466m (br.), 2959s, 2875m, 2837m, 2178w, 1743s, 1613m, 1587m, 1514s, 1464m, 1441m, 1370m,

1301m, 1250s, 1172m, 1151m, 1089s, 1041s, 913w, 844m. ¹H-NMR (500 MHz, CDCl₃): 7.28 ± 7.19 (m, 16 ar-

om. H); 6.88 ± 6.80 (m, 16 arom. H), 5.18 ± 5.12 (m, M of ABMX, virtual coupling, J_MXꢁ 10.6, J_AMꢁ 9.4,

H

C(3')); 4.89 (d, J 11.0, ArCH); 4.82 ± 4.78 (m, AB of H C(1'), H C(2'), 3 ArCH); 4.75 (d, J 10.8,

ArCH); 4.71 (d, J 10.4, ArCH); 4.63 (d, J 10.9, ArCH); 4.62 (d, J 7.8, H C(1''')); 4.60 (d, J 11.0,

ArCH); 4.32 (dd, J 12.0, 2.8, H_aC(6')); 4.24 (dd, J 12.0, 5.0, H_bC(6')); 4.01 (d, J 9.5, H C(3)); 3.96

(dd, J 12.0, 2.5, H_aC(8)); 3.91 (d, J 9.5, H C(5'')); 3.89 (t, J ꢁ 9.8, H C(6)); 3.88 (br. d, J ꢁ 12.0,

H_bC(8)); 3.85 (br. d, J ꢁ 11.9, H_aC(10'')); 3.85 (t, J ꢁ 9.2, H C(8'')); 3.81 (s, MeO); 3.80 (s, 2 MeO); 3.78

(s, MeO); 3.81 ± 3.78 (m, H_bC(10'')); 3.76 ± 3.74 (m, addn. of D₂O ! 3.76, dd, J 12.0, 2.2, H_aC(6''')); 3.59

(ddd, J 10.4, 5.0, 2.8, H C(5')); 3.57 ± 3.49 (m, addn. of D₂O ! 3.56, t, J ꢁ 9.6, H C(3'''), ! 3.51, dd, J 11.9,

6.0, H_bC(6''')); 3.49 (t, J ꢁ 9.0, H C(5)); 3.43 (t, J ꢁ 9.4, H C(4)); 3.42 (t, J ꢁ 9.0, H C(7'')); 3.40 (t, J ꢁ 8.9,

H

C(6'')); 3.33 ± 3.30 (m, addn. of D₂O ! 3.32, ddd, J 10.2, 5.8, 2.2, H C(5''')); 3.23 (br. t, addn. of D₂O !

t, J ꢁ 8.6, H C(2''')); 3.21 (br. dt, J ꢁ 10.0, 1.5, H C(7)); 3.17 (br. s, exchanged with D₂O, HO C(2''')); 3.09 ±

3.07 (m, addn. of D₂O ! 3.08, br. ddd, J ꢁ 9.8, 2.2, 1.3, H C(9'')); 2.92 (t, J ꢁ 10.3, H C(4')); 2.60 (br. s,

exchanged with D₂O, HO C(3''')); 2.52 (t, J ꢁ 10.3, H C(4''')); 2.02 (s, Ac); 2.01 (s, Ac); 1.98 (s, Ac); 1.88

(m, exchanged with D₂O, HO C(6''')); 1.65 (sept., J 6.9, Me₂CH); 1.64 (sept., J 6.9, Me₂CH); 0.92 (d, J

6.9, MeCH); 0.91 (d, J 6.9, MeCH); 0.90 (d, J 6.9, MeCH); 0.89 (d, J 6.9, MeCH); 0.869 (s, MeCSi); 0.866

(s, MeCSi); 0.857 (s, 2 MeCSi); 0.17 (s, Me₃Si); 0.153 (s, MeSi), 0.147 (s, 2 MeSi); 0.135 (s, MeSi). ¹³C-NMR

(125 MHz, CDCl₃): 170.46 (s,CO); 169.64 (s,CO); 169.51 (s,CO); 159.48 (s); 159.27 (s); 159.22 (s);

158.99 (s); 131.39 (s); 130.18 (s); 130.43 (s); 130.01 (s); 129.93 (2d); 129.79 (2d); 129.11 (2d); 128.78 (2d); 113.93

(2d); 113.82 (2d); 113.67 (2d); 113.57 (2d); 102.92 (s, CꢀCSi); 101.98 (d, C(1''')); 99.94 (d, C(1')); 90.43

(s, CꢀCSi); 83.99 (d); 83.22 (d); 81.68 (d); 81.47 (d); 79.60 (d); 79.43 (d); 76.39 (d); 75.92 (s, CꢀCBr); 75.58 (d);

75.34 (d); 75.33 (s, C(1'')); 75.15 (t, 2 ArCH₂); 75.12 (d); 75.12 (t, ArCH₂); 74.71 (t, ArCH₂); 74.56 (d); 73.93

(s, C(4'')); 72.56 (d); 72.45 (d); 72.41 (d); 70.03 (d, C(5'')); 69.74 (d, C(3)); 69.48 (s, C(3'')); 68.74 (s, C(2''));

64.01 (t); 63.04 (t); 61.57 (t); 61.13 (t); 55.32 (q, MeO); 55.27 (q, 2 MeO); 55.25 (q, MeO); 43.63 (s, CꢀCBr);

38.01 (d, C(4''')); 36.77 (d, C(4')); 34.27 (d, MeCH); 34.08 (d, MeCH); 25.31 (s, MeCSi); 25.23 (s, MeCSi);

20.74 (q, Me); 20.67 (q, Me); 20.54 (q, Me); 20.54 (q, MeCH); 20.46 (q, MeCH); 20.34 (q, MeCH); 20.23

(q, MeCH); 18.75 (q, MeCSi); 18.70 (q, MeCSi); 18.59 (q, MeCSi); 18.51 (q, MeCSi); 0.30 (q, Me₃Si); 2.86

(q, MeSi); 2.90 (q, MeSi); 3.18 (q, MeSi); 3.23 (q, MeSi). MALDI-TOF-MS: 1796 ([M K] ), 1780

([M Na] ). Anal. calc. for C₈₉H₁₂₃BrO₂₅Si₃(1757.10): C 60.84, H 7.06, Br 4.55; found: C 60.25, H 6.72, Br 4.28.

4-Deoxy-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-

bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-

b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethyl-

silyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-

1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-

(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxy-

benzyl)-8-O-(thexyldimethylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (41). A degassed soln. of

40 (383mg, 0.217 mmol), 39 (340mg, 0.213 mmol), [Pd₂(dba)₃] (5.9 mg, 3 mol-%), CuI (1.2 mg, 3 mol-%), and

P(furyl)₃(3.0 mg, 6 mol-%) in DMSO (5 ml) was treated at r.t. with Et₃N (0.1 ml), stirred for 2.5 h, poured into

ice-cold sat. NH₄Cl soln. (5 ml), and worked up (CH₂Cl₂). FC (CH₂Cl₂! CH₂Cl₂/MeOH/toluene 60 : 1 : 2 !

120 : 4 : 3) gave 41 (376.4 mg, 54%). Colourless oil. R_f(CH₂Cl₂/toluene/MeOH 30 : 1 : 1) 0.21. [a]_D²⁵

1.5 (c

1.0, CHCl₃). IR (CCl₄): 3573s (br.), 3477s (br.), 2957s, 2880m, 2831m, 2805m, 2178w, 1755s, 1644w, 1611s,

1586m, 1514s, 1366m, 1298m, 1250s, 1173m, 1149m, 1089s, 1039s, 913w, 832s. ¹H-NMR (300 MHz, CDCl₃): 7.38±

7.18 (m, 16 arom. H); 6.78±6.94 (m, 16 arom. H); 5.19±5.12 (m, M of ABMX, virtual coupling, J_MXꢁ 10.6, J_AMꢁ 9,6,

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Helvetica Chimica Acta ± Vol. 81 (1998)

H

C(3^II)); 4.92 ± 4.52 (m, H C(1^II), H C(2^II), H C(1^IV), H C(1^VI), H C(1^VIII), 16 ArCH); 4.31 (dd, J ꢁ

11.5, 2.2, H_aC(6^II)); 4.24 (dd, J 11.8, 4.4, H_bC(6^II)); 4.02 (d, J 9.3,

H

C(3^I)); 4.00 (d, J 9.0,

H

C(5^III)); 3.97 ± 3.67 (m, 19 H); 3.81 (s, MeO); 3.80 (s, MeO); 3.79 (s, 3 MeO); 3.787 (s, 3 MeO); 3.66 ±

3.18 (m, 26 H, addn. of D₂O ! signal changed, 2 H exchanged); 3.12 ± 3.04 (m, addn. of D₂O ! 1 H

exchanged, ! 3.08 br. d, J ꢁ 10, 1 H); 2.93 (t, J ꢁ 10.6, H C(4^II)); 2.84 (br. s, exchanged with D₂O, OH); 2.65

(br. s, exchanged with D₂O, 2 OH); 2.65 (t, J ꢁ 10.4, H C(4^IV), H C(4^VI)); 2.48 (t, J ꢁ 10.4, H C(4^VIII)); 2.02

(s, Ac); 2.01 (s, Ac); 1.98 (s, Ac); 1.78 ± 1.55 (m, addn. of D₂O ! 3 H exchanged, 4 Me₂CH); 0.95 ± 0.78

(m, 16 Me); 0.33 (s, Me₃Ge); 0.17 (s, Me₃Si); 0.18 ± 0.12 (m, 8 MeSi). ¹³C-NMR (100 MHz, CDCl₃): 170.46

(s, CO); 169.64 (s, CO); 169.51 (s, CO); 159.49 (s); 159.41 (2s); 159.27 (2s); 159.23 (2s); 158.99 (s); 131.39

(2s); 130.85 (2s); 130.76 (2s); 130.44 (2s); 129.99 ± 128.75 (several d); 113.93 (4d); 113.84 (4d); 113.81 (4d);

113.68 (2d); 113.57 (2d); 102.93 (s, CꢀCSi); 101.99 (d, C(1^IV), C(1^VIII)); 101.95 (d, C(1^VI)); 100.02

(s, CꢀCGe); 99.95 (d, C(1^II)); 90.44 (s,CꢀCSi); 90.06 (s, CꢀCGe); 84.06 (d); 83.97 (2d); 83.23 (d); 81.68

(2d); 81.51 (2d); 79.68 (d); 79.56 (d); 79.43 (2d); 76.40 (d); 76.26 (d); 76.20 (s); 75.72 (2d); 75.68 (d); 75.64 (2d);

75.33 (t, 3 ArCH₂); 75.33 (d); 75.15 (t, 3 ArCH₂); 75.15 (d); 75.08 (2d); 74.91 (2d); 74.77 (s); 74.71

(t, 2 ArCH₂); 74.46 (d); 73.96 (s); 72.56 (d); 72.45 (d); 72.41 (d); 70.04 (2d); 69.81 (s); 69.74 (2d); 69.50 (s);

68.74 (s); 68.52 (s); 68.49 (s); 64.02 (t); 63.36 (2t); 63.00 (2t); 61.51 (2t); 61.14 (t); 38.62 (d, C(4^VIII)); 37.64

(d, C(4^VI)); 37.50 (d, C(4^IV)); 36.78 (d, C(4^II)); 34.27 (d, MeCH); 34.09 (d, 3 MeCH); 25.35 (s, MeCSi); 25.30

(s, MeCSi); 25.28 (s, MeCSi); 25.24 (s, MeCSi); 20.75 (q, Me); 20.67 (q, Me); 20.54 (q, 2 Me); 20.47 (q, 3 Me);

20.33 (q, Me); 20.24 (q, 3 Me); 18.76 (q, Me); 18.72 (q, 3 Me); 18.60 (q, Me); 18.53 (q, 3 Me);

0.11

(q, Me₃Ge); 0.30 (q, Me₃Si); 2.79 (q, 2 MeSi); 2.85 (q, MeSi); 2.89 (q, 2MeSi); 3.18 (q, MeSi);

3.23 (q, 2 MeSi); 3s for CꢀC not observed or hidden. MALDI-TOF-MS: 3296 ([M Na] ). Anal. calc. for

C

₁₇₂H₂₄₀GeO₄₇Si₅(3272.82): C 63.12, H 7.39; found: C 62.95, H 7.27.

4-Deoxy-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-

bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-

b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethyl-

silyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-

1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-

(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-

(thexyldimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (42), 4-Deoxy-4-C-ethynyl-b-d-glucopyranosyl-(1 ! 8)-5,9-

anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-

diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-me-

thoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-gluco-

pyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-

glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-

4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (43), and 4-Deoxy-4-C-

[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxy-

benzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyra-

nosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glyc-

ero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetra-

deoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-

C)-2,3-di-O-acetyl-4-deoxy-b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-

8-O-(thexyldimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (44). A soln. of 41 (325 mg, 99.3 mmol) in THF (6 ml)

was treated dropwise at 08 with cold sat. K₂CO₃soln. in MeOH (0.3 ml), stirred for 10 h at 08, neutralized with

Amberlite IR-120 (H form), filtered, and evaporated. FC (CHCl₃! CHCl₃/MeOH/toluene 60 :1 : 2 !

120 : 3 : 4) gave 44 (19.5 mg, 7%), 42 (168 mg, 55%) and 43 (7.2 mg, 2%) as colourless oils.

Data of 42: R_f(CH₂Cl₂/toluene/MeOH 20 :1:1) 0.24. [a]²_D⁵ 6.2 (c 2, CHCl₃). IR (CCl₄): 3589m, 3411m

(br.), 3311m, 3007m, 2955s, 2922m, 2872m, 2255w, 2167w, 1613s, 1514s, 1465m, 1364m, 1301m, 1251s, 1150m,

1089s, 1035s, 912m, 826s. ¹H-NMR (300 MHz, CDCl₃): 7.36 ± 7.18 (m, 16 arom. H); 6.86 ± 6.78 (m, 16 arom. H);

4.94 ± 4.50 (m, H C(1^II), H C(1^IV), H C(1^VI), H C(1^VIII), 16 ArCH); 4.18 ± 3.66 (m, addn. of D₂O ! signal

changed, 17 H); 3.81 (s, MeO); 3.78 (s, 2 MeO); 3.778 (s, 2 MeO); 3.775 (s, MeO); 3.76 (s, MeO); 3.74

(s, MeO); 3.64 ± 3.10 (m, addn. of D₂O ! signal changed, 3 H exchanged, 31 H); 2.80 (br. s, exchanged with

D₂O, OH); 2.65 (t, J ꢁ 10.4,

H

C(4^VI)); 2.62 (br. t, J ꢁ 10.3,

H

C(4^II),

H

C(4^IV)); 2.50 (d, J 2.0,

HCꢀC C(3^I)); 2.47 (t, J ꢁ 10.4, H C(4^VIII)); 2.14 (br. s, exchanged with D₂O, 4 OH); 2.02 (d, J 3.0,

exchanged with D₂O, OH); 1.92 (br. s, exchanged with D₂O, 3 OH); 1.70 ± 1.54 (m, 4 Me₂CH); 0.92 ± 0.80

(m, 16 Me); 0.33 (s, Me₃Ge); 0.18 ± 0.10 (m, 8 MeSi). ¹³C-NMR (100 MHz, CDCl₃): 159.37 (2s); 159.32 (2s);

159.24 (2s); 159.20 (2s); 130.88 (2s); 130.76 (4s); 130.19 (2s); 130.09 ± 128.99 (several d); 113.92 ± 113.78

Helvetica Chimica Acta ± Vol. 81 (1998)

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(several d); 101.98 (d, C(1^IV), C(1^VIII)); 101.90 (d, C(1^II), C(1^VI)); 100.21 (s, CꢀCGe); 89.93 (s, CꢀCGe); 83.91

(2d); 83.84 (2d); 81.79 (2d); 81.68 (2d); 81.49 (d); 81.04 (d, CꢀCH); 79.50 (4d); 75.76 (2d); 75.62 (2d); 75.27

(t, ArCH₂); 75.27 (2d); 75.27 (t, 2 ArCH₂); 75.21 (t, 2 ArCH₂); 75.11 (4d); 74.95 (2d); 74.80 (s, CꢀCH); 74.51

(2d); 74.38 (2d); 73.75 (s); 69.88 (2d); 69.66 (s); 69.43 (d); 68.35 (s); 63.29 (2t); 63.05 (2t); 61.58 (2t); 61.46 (2t);

55.29 (q, 5 MeO); 55.26 (2q, MeO); 55.24 (q, MeO); 38.60 (d, C(4^VIII)); 37.88 (d, C(4^IV), C(4^VI)); 37.72

(d, C(4^II)); 34.11 (d, 2 MeCH); 34.09 (d, 2 MeCH); 25.27 (s, 8 CSi); 20.49 (q, 2 MeCH); 20.48 (q, 3 MeCH);

20.25 (q, 3 MeCH); 18.74 (q, 4 MeCSi); 18.54 (q, 4 MeCSi); 0.11 (q, Me₃Ge);

2.78 (q, MeSi);

2.82

(q, 2 MeSi); 2.85 (q, MeSi); 3.21 (q, 3 MeSi); 3.25 (q, MeSi); 9s for CꢀC not observed or hidden.

MALDI-TOF-MS: 3098 ([M Na] ). Anal. calc. for C₁₆₃H₂₂₆GeO₄₄Si₄(3074.50): C 63.68, H 7.41; found:

C 63.56, H 7.50.

Data of 43: R_f(CH₂Cl₂/toluene/MeOH 20 :1:1) 0.20. IR (CHCl₃): 3605m, 3400m (br.), 3308m, 3007m,

2960s, 2878m, 2177w, 1613s, 1442m, 1366m, 1301m, 1248s, 1173m, 1150m, 1089s, 1036s, 931m, 910m, 874m, 826s.

MALDI-TOF-MS for C₁₆₀H₂₁₈O₄₄Si₄(2957.84): 2981 ([M Na] ), 2997 ([M K] ).

Data of 44: R_f(CH₂Cl₂/toluene/MeOH 20 :1:1) 0.29. IR (CHCl₃): 3603m, 3400m (br.), 3306m, 3007m,

2959s, 2878m, 2178w, 1754m, 1613s, 1514s, 1465m, 1377w, 1302m, 1248s, 1088s, 1035s, 827m. ¹H-NMR (500 MHz,

CDCl₃): 7.30 ± 7.20 (m, 16 arom. H); 6.90 ± 6.80 (m, 16 arom. H); 5.15 (dd, J 10.7, 8.8, H C(3^II)); 4.90 ± 4.70,

4.66 ± 4.63 (2m, 16 ArCH, H C(1^II), H C(1^IV), H C(1^VI), H C(1^VIII), H C(2^II)); 4.02 (br. d, J ꢁ 9.3,

H

C(5^III), H C(5^V), H C(5^VII)); 4.03 ± 3.85 (m, addn. of D₂O ! signal changed, 14 H); 3.81 (s, MeO); 3.80

(s, MeO); 3.792 (s, MeO); 3.790 (s, 2 MeO); 3.788 (s, MeO); 3.786 (s, MeO); 3.783 (s, MeO); 3.81 ± 3.74

(m, addn. of D₂O ! signal changed, 2 H); 3.63 ± 3.39 (m, addn. of D₂O ! signal changed, 17 H); 3.37 ± 3.32

(m, addn. of D₂O ! signal changed, 3 H); 3.28 ± 3.20 (m, addn. of D₂O ! signal changed, 6 H, 2 H exchanged);

3.12 (br. dt, J ꢁ 10.0, 2.7, 1 H); 3.02 (br. s, exchanged with D₂O, 1 OH); 2.86 (t, J ꢁ 10.5, H C(4^II)); 2.72 (br. s,

exchanged with D₂O, 2 OH); 2.66 (br. t, J ꢁ 10.6, H C(4^IV), H C(4^VI)); 2.58 (br. d, J ꢁ 2.1, exchanged with

D₂O, OH); 2.48 (t, J ꢁ 10.5, H C(4^VIII)); 2.47 (d, J 2.1, HCꢀC C(3^I)); 2.02 (s, Ac); 2.01 (s, Ac); 1.91 (br. s,

exchanged with D₂O, OH); 1.79 (br. s, exchanged with D₂O, 2 OH); 1.67 ± 1.58 (m, 4 Me₂CH, 1 H exchanged

with D₂O); 0.92 ± 0.84 (m, 16 Me); 0.33 (s, Me₃Ge); 0.20 ± 0.07 (m, 8 MeSi). ¹³C-NMR (125 MHz, CDCl₃):

169.67 (s, CO); 169.56 (s, CO); 159.49 (s); 159.41 (s); 159.32 (2s); 159.36 (s); 159.22 (3s); 131.02 (s); 130.86

(2s); 130.77 (3s); 130.28 (2s); 129.98 ± 128.74 (several d); 113.93 (5d); 113.84 (6d); 113.80 (5d); 102.01

(d, C(1^IV), C(1^VI)); 101.96 (d, C(1^VIII)); 99.96 (s, CꢀCGe); 99.87 (d, C(1^II)); 90.09 (s, CꢀCGe); 84.10 (d); 83.99

(2d); 83.50 (d); 81.84 (d); 81.60 (2d); 81.52 (2d); 81.02 (d, CꢀCH); 79.69 (d); 79.65 (d); 79.54 (2d); 79.37 (s);

78.10 (s); 76.45 (s); 76.15 (d); 75.68 (br., 3d); 75.34 (2t); 75.34 (d); 75.29 (2d); 75.11 (3t); 75.07 (2t); 74.93 (t);

74.82 (2d); 75.75 (s, CꢀCH); 74.74 (d); 74.44 (2d); 74.30 (s); 73.75 (s); 73.56 (s); 72.71 (d); 72.57 (d); 70.05

(2d); 69.82 (s); 69.75 (s); 69.60 (d); 69.48 (d); 69.38 (d); 68.56 (s); 68.55 (s); 68.51 (s); 63.36 (2t); 62.99 (2t);

62.72 (t); 61.59 (2t); 60.97 (t); 55.31 (q, 5 MeO); 55.29 (q, 3MeO); 38.61 (d, C(4^VIII), C(4^IV)); 37.62 (d, C(4^VI));

36.27 (d, C(4^II)); 34.20 (d, 2MeCH); 34.09 (d, 2MeCH); 25.30 (s, MeCSi); 25.28 (s, MeCSi); 25.20 (s, 2 MeCSi);

20.75 (q, Me); 20.57 (q, Me); 20.51 (q, 2 Me); 20.47 (q, 3 Me); 20.23 (q, 3 Me); 18.72 (q, 3 Me); 18.53 (q, 5 Me);

0.11 (q, Me₃Ge);

₁₆₇H₂₃₀GeO₄₆Si₄(3158.13): 3181 ([M Na] ), 3197 ([M K] ).

4-Deoxy-2,3,6-tris-O-(triethylsilyl)-4-C-[(trimethylgermyl)ethynyl]-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-

2.80 (q, 3 MeSi);

2.94 (q, MeSi);

3.25 (q, 4 MeSi). MALDI-TOF-MS for

C

1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-

1-yl-(1 ! 4-C)-4-deoxy-2,3,6-tris-O-(triethylsilyl)-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-

6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-de-

oxy-2,3,6-tris-O-(triethylsilyl)-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxy-

benzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-

b-d-glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-

1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (45). A soln. of 41 (200 mg, 0.061 mmol) and 1H-imidazole

(166.4 mg, 2.44 mmol) in DMF (4 ml) was treated at 08 with Et₃SiCl (193.1 ml, 1.83 mmol), stirred at r.t. for 5 h,

poured into ice-water (5 ml) and worked up (hexane). FC (hexane/Et₃N 1 : 0.01 ! hexane/AcOEt/Et₃N

9 : 2 : 0.01) gave 45 (241 mg, 92%). Colourless oil. R_f(hexane/AcOEt 3 : 1) 0.71. [a]_D²⁵

29.3 (c 2, CHCl₃). IR

(CCl₄): 2956s, 2911s, 2876s, 2166w, 1759m, 1613m, 1514s, 1464m, 1366m, 1250s, 1173m, 1087s, 909m, 832s.

¹H-NMR (300 MHz, CDCl₃): 7.38 ± 7.18 (m, 16 arom. H); 6.78 ± 6.94 (m, 16 arom. H); 5.20 ± 5.10 (m, M of

ABMX, virtual coupling, J_MXꢁ 10.6, J_AMꢁ 9.3, H C(3^II)); 4.98 (d, J 10.6, ArCH); 4.95 (br. d, J ꢁ 10.0,

2 ArCH); 4.89 (d, J 11.2, ArCH); 4.80 ± 4.58 (m, H C(1^II), H C(2^II), H C(1^IV), H C(1^VI), H C(1^VIII),

12 ArCH); 4.44 ± 4.36 (m, 2 H); 4.31 (dd, J 11.8, 2.8, H_aC(6^II)); 4.23 (dd, J 11.8, 4.7, H_bC(6^II));

4.10 ± 3.73 (m, 20 H); 3.80 (s, MeO); 3.797 (s, 2 MeO); 3.793 (s, 2 MeO); 3.788 (s, 3 MeO); 3.66 ± 3.54 (m,

5 H); 3.52 ± 3.42 (m, 10 H); 3.32 ± 3.12 (m, 6 H); 3.08 (br. d, J ꢁ 10.0, 1 H); 2.92 (t, J ꢁ 10.6, H C(4^II)); 2.64

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Helvetica Chimica Acta ± Vol. 81 (1998)

(t, J ꢁ 10.3, H C(4^IV)); 2.63 (t, J ꢁ 10.4, H C(4^VI)); 2.44 (t, J ꢁ 10.6, H C(4^VIII)); 2.02 (s, Ac); 2.00 (s, Ac);

1.97 (s, Ac); 1.72 ± 1.52 (m, 4 Me₂CH); 1.00 ± 0.80 (m, 129 H); 0.78 ± 0.52 (54 H); 0.33 (s, Me₃Ge); 0.17

(s, Me₃Si); 0.19 ± 0.09 (m, 8 MeSi). ¹³C-NMR (125 MHz, CDCl₃): 170.46 (s, CO); 169.65 (s, CO); 169.52

(s, CO); 159.35 (s); 159.32 (s); 159.27 (s); 159.02 (2s); 159.00 (2s); 158.97 (s); 131.64 (s); 131.47 (s); 131.44 (s);

131.39 (s); 130.45 (s); 130.38 (s); 130.30 (s); 130.25 (s); 130.12 ± 129.13 (several d); 113.82 (s); 113.75 (s); 113.73

(s); 113.68 (s); 113.58 (s); 113.41 (2s); 113.39 (s); 104.23 (s, CꢀCGe); 102.94 (s, CꢀCSi); 101.34 (d, C(1^IV),

C(1^VIII)); 101.28 (d, C(1^VI)); 99.94 (d, C(1^II)); 90.42 (s, CꢀCSi); 88.56 (s, CꢀCGe); 83.23 (2d); 83.13 (2d);

83.08 (d); 83.01 (d); 81.74 (d); 81.69 (2d); 81.31 (d); 79.92 (d); 79.84 (2d); 79.74 (d); 79.45 (d); 78.87 (s); 78.83

(s); 77.97 (2d); 77.29 (d); 76.50 (d); 76.44 (2d); 76.39 (d); 76.21 (d); 75.78 (s); 75.30 (d); 75.30 (t, ArCH₂); 75.15

(t, ArCH₂); 74.72 (t, 2 ArCH₂); 74.64 (t, 2 ArCH₂); 74.59 (t, ArCH₂); 74.52 (t, ArCH₂); 73.50 (s); 72.60 (2d);

72.49 (d); 72.40 (d); 70.03 (2d); 69.74 (2d); 69.54 (s); 69.50 (s); 68.94 (s); 68.70 (s); 68.68 (s); 64.06 (t); 63.77

(3t); 61.15 (2t); 61.02 (2t); 55.28 (q, MeO); 55.27 (q, MeO); 55.26 (q, 2 MeO); 55.25 (q, 2 MeO); 55.18

(q, 2 MeO); 39.94 (d, C(4^VII)); 39.66 (d, C(4^IV), C(4^VI)); 36.82 (d, C(4^II)); 34.31 (d, MeCH); 34.29 (d, MeCH);

34.27 (d, MeCH); 34.24 (d, MeCH); 25.24 (s, MeCSi); 25.23 (s, 3 MeCSi); 20.76 (q, Me); 20.68 (q, Me); 20.55

(q, 3 Me); 20.54 (q, 2 Me); 20.34 (q, Me); 20.28 (q, Me); 20.26 (q, 2 Me); 18.79 (q, Me); 18.76 (q, 3 Me); 18.60

(q, Me); 18.56 (q, Me); 18.54 (q, 2 Me); 7.09 (q, 6 Me); 7.07 (q, 4 Me); 7.04 (q, 4 Me); 7.01 (q, 6 Me); 6.91

(q, 3 Me); 6.88 (q, 4 Me); 5.59 (4t); 5.50 (5t); 5.34 (6t); 4.50 (4t); 4.42 (4t); 4.41 (4t); 0.30 (q, Me₃Si); 0.44

(q, Me₃Ge); 2.84, 2.86, 2.88, 2.90, 3.17, 3.40, 3.49, 3.56 (8q, 8 MeSi); 3s for CꢀC not observed or

hidden. MALDI-TOF-MS for C₂₂₆H₃₆₆GeO₄₇Si₁₄(4301.20): 4324 ([M Na] ).

4-C-(Bromoethynyl)-4-deoxy-2,3-6-tris-O-(triethylsilyl)-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-

tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-

(1 ! 4-C)-4-deoxy-2,3,6-tris-O-(triethylsilyl)-b-d-glucopyranosyl-(1 ! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-

O-(4-methoxybenzyl)-10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-4-deoxy-

2,3,6-tris-O-(triethylsilyl)-b-d-glucopyranosyl-(1! 8)-5,9-anhydro-1,2,3,4-tetradeoxy-6,7-bis-O-(4-methoxybenzyl)-

10-O-(thexyldimethylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 4-C)-2,3,6-tri-O-acetyl-4-deoxy-b-d-

glucopyranosyl-(1 ! 6)-3,7-anhydro-1,2-dideoxy-4,5-bis-O-(4-methoxybenzyl)-8-O-(thexyldimethylsilyl)-1-C-

(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (46). A soln. of 45 (57.8 mg, 13.4 mmol) and NBS (3.1 mg,

17.5 mmol) in acetone (0.5 ml), was treated with CuBr (0.6 mg, 30 mol-%), stirred at r.t. for 8 h, poured into ice-

cold sat. Na₂S₂O₃soln. (2 ml), and worked up (CH₂Cl₂). Drying for 4 h under h.v. gave 46 (49.3 mg, 86%) as a

colourless oil which was directly used for the next step. R_f(hexane/AcOEt 3 : 1) 0.71. [a]_D²⁵

CHCl₃). IR (CCl₄): 2956s, 2911s, 2876s, 2280w, 2166w, 2077w, 1759m, 1613m, 1587m, 1514s, 1464m, 1414m,

1366m, 1301m, 1250s, 1173m, 1117s, 1087s, 1041s, 912m, 832s. ¹H-NMR (300 MHz, CDCl₃): 7.38 ± 7.18

27 (c 1.1,

(m, 16 arom. H); 6.78 ± 6.94 (m, 16 arom. H); 5.20 ± 5.10 (m, M of ABMX, virtual coupling, J_MXꢁ 10.6, J_AM

ꢁ

9.3, H C(3^II)); 5.00 (d, J 10.5, ArCH); 4.96 (br. d, J ꢁ 11.0, 2 ArCH); 4.89 (d, J 11.2, ArCH); 4.80 ± 4.57

(m, H C(1^II), H C(2^II), H C(1^IV), H C(1^VI), H C(1^VIII), 12 ArCH); 4.45 ± 4.36 (m, 4 H); 4.32 (dd, J

11.8, 2.9, H_aC(6^II)); 4.24 (dd, J 11.8, 4.7, H_bC(6^II)); 4.06 ± 3.70 (m, 18 H); 3.81 (s, MeO); 3.80 (s, 4MeO);

3.79 (s, 3 MeO); 3.66 ± 3.54 (m, 5 H); 3.52 ± 3.30 (m, 10 H); 3.32 ± 3.10 (m, 6 H); 3.08 (br. d, J ꢁ 11.0, 1 H); 2.92

(t, J ꢁ 10.5, H C(4^II)); 2.65 (t, J ꢁ 10.3, H C(4^IV)); 2.64 (t, J ꢁ 10.4, H C(4^VI)); 2.54 (t, J ꢁ 10.6, H C(4^VIII));

2.02 (s, Ac); 2.00 (s, Ac); 1.98 (s, Ac); 1.72 ± 1.54 (m, 4 Me₂CH); 1.00 ± 0.81 (m, 129 H); 0.78 ± 0.54 (54 H); 0.18

(s, Me₃Si); 0.19 ± 0.09 (m, 8 MeSi). ¹³C-NMR (125 MHz, CDCl₃): 170.46 (s, CO); 169.65 (s, CO); 169.53

(s, CO); 159.35 (2s); 159.27 (2s); 159.01 (4s); 131.50 (s); 131.46 (s); 131.43 (s); 131.38 (s); 130.45 (s); 130.32

(s); 130.24 (s); 1 arom. s not observed or hidden; 130.10 ± 129.13 (several d); 113.81 ± 113.41 (several d); 102.93

(s, CꢀCSi); 101.34 (d, C(1^IV), C(1^VIII)); 101.28 (d, C(1^VI)); 99.93 (d, C(1^II)); 90.42 (s, CꢀCSi); 83.23 (d);

83.07 (2d); 83.01 (d); 81.74 (2d); 81.68 (2d); 81.30 (d); 79.92 (d); 79.75 (d); 79.45 (2d); 79.16 (d); 78.88 (s);

77.96 (2d); 77.43 (2d); 76.44 (2d); 76.38 (s, CꢀCBr); 76.35 (2d); 76.20 (d); 75.77 (s); 75.31 (d); 75.15

(t, ArCH₂); 74.72 (t, 2 ArCH₂); 74.64 (t, 2 ArCH₂); 74.59 (t, ArCH₂); 74.56 (t, ArCH₂); 74.52 (t, ArCH₂); 74.32

(s); 73.50 (s); 72.60 (2d); 72.49 (d); 72.39 (d); 70.03 (2d); 69.74 (2d); 69.54 (s); 68.94 (s); 68.67 (s); 64.05 (t);

63.87 (2t); 63.77 (2t); 61.14 (2t); 61.01 (t); 55.28 (q, MeO); 55.27 (q, 2 MeO); 55.25 (q, 2 MeO); 55.18

(q, 3MeO); 42.92 (s, CꢀCBr); 40.08 (d, C(4^VIII)); 39.65 (d, C(4^IV), C(4^VI)); 36.81 (d, C(4^II)); 34.31 (d, MeCH);

34.29 (d, MeCH); 34.27 (d, MeCH); 34.23 (d, MeCH); 25.24 (s, MeCSi); 25.22 (s, 3 MeCSi); 20.76 (q, Me);

20.68 (q, Me); 20.53 (q, 3 Me); 20.34 (q, 2 Me); 20.26 (q, 4 Me); 18.76 (q, 2 Me); 18.59 (q, 4 Me); 18.56 (q, Me);

18.53 (q, 3 Me); 7.08 (q, 8 Me); 7.03 (q, 5 Me); 7.01 (q, 7 Me); 6.88 (q, 7 Me); 5.58 (t); 5.50 (7t); 5.47 (2t); 5.34

(8t); 4.50 (t); 4.45 (2t); 4.41 (3t); 4.40 (3t); 0.30 (q, Me₃Si); 2.86, 2.88, 2.90, 3.17, 3.20, 3.41,

3.49, 3.56 (8q, 8 MeSi); 5s for CꢀC not observed or hidden. MALDI-TOF-MS for C₂₂₃H₃₅₇BrO₄₇Si₁₄

(4263.41): 4287 ([M Na] ).

Article Doi

Oligosaccharide analogues of polysaccharides: Part 15: Oligomers of cellobiose-derived dialkynes and first crystal structure of an anomeric pair of trichloroacetimidates

DOI: 10.1002/(SICI)1522-2675(19981216)81:12<2157::AID-HLCA2157>3.0.CO;2-4

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Full text of DOI:10.1002/(SICI)1522-2675(19981216)81:12<2157::AID-HLCA2157>3.0.CO;2-4

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