Oligosaccharide analogues of polysaccharides: Part 16: Cross-coupling of partially protected dialkynyl monosaccharides

Article abstract of DOI:10.1002/(SICI)1522-2675(19990210)82:2<143::AID-HLCA143>3.0.CO;2-0

The dependency of the cross-coupling of orthogonally C-protected dialkynyl monosaccharides on the nature of the coupling partners has been studied. The required dialkyne 5 was synthesized from levoglucosan in six steps and 39% overall yield and transformed into 7, 10, 12, 13, and 14 by orthogonal C-deprotection and bromination (Scheme 1). Optimization of the conditions of their cross-coupling to 16 showed that yields were higher for the coupling of the propargylic bromoalkyne 10 than for the homopropargylic bromoalkyne 14 (Scheme 2). Deprotection of 16 gave the nano-crystalline dimer 20. To obtain more highly crystalline products, the monomers 7 and 13 were coupled with 1-iodo-4-nitrobenzene to the arylated monomers 21 and 24 (Scheme 3). The 4-NO₂C₆H₄ substituent lowered the yield of the dimerizations to the mono- and diarylated dimers 26-28 (Scheme 4) but had no effect on crystallinity.

Full text of DOI:10.1002/(SICI)1522-2675(19990210)82:2<143::AID-HLCA143>3.0.CO;2-0

Helvetica Chimica Acta ± Vol. 82 (1999)
143
Oligosaccharide Analogues of Polysaccharides
Part 16
Cross-Coupling of Partially Protected Dialkynyl Monosaccharides
1
by Tanja Verena Bohner, Renaud Beaudegnies ), and Andrea Vasella*
Laboratorium für Organische Chemie, ETH-Zentrum, Universitätstrasse 16, CH-8092 Zürich
The dependency of the cross-coupling of orthogonally C-protected dialkynyl monosaccharides on the
nature of the coupling partners has been studied. The required dialkyne 5 was synthesized from levoglucosan in
six steps and 39% overall yield and transformed into 7, 10, 12, 13, and 14 by orthogonal C-deprotection and
bromination (Scheme 1). Optimization of the conditions of their cross-coupling to 16 showed that yields were
higher for the coupling of the propargylic bromoalkyne 10 than for the homopropargylic bromoalkyne 14
(Scheme 2). Deprotection of 16 gave the nano-crystalline dimer 20. To obtain more highly crystalline products,
the monomers 7 and 13 were coupled with 1-iodo-4-nitrobenzene to the arylated monomers 21 and 24
(Scheme 3). The 4-NO2C6H4 substituent lowered the yield of the dimerizations to the mono- and diarylated
dimers 26 ± 28 (Scheme 4) but had no effect on crystallinity.
Introduction. ± The binomial synthesis of oligomeric O-benzyl-protected ꢀacetyl-
enocellulosesꢁ [1], requiring selective C-deprotection, C-bromination, and cross-
coupling, proceeded in excellent yields up to an octamer [2], while the yield of the
hexadecamer dropped to 6% [3], presumably due to problems of solubility. This raises
questions about the number and kind of OH-protecting groups that are required to
provide soluble oligomers and about their influence on the individual steps of the
binomial cycle and especially on cross-coupling. Exploratory experiments of Alzeer [4]
indicated that the results of the cross-coupling may also depend upon the position of the
halo substituent.
We wished to evaluate the influence on the cross-coupling of the nature and
position of the halide substituent of the haloalkynes and of C-aryl groups that might
favour the tendency of the products to crystallize. To investigate these aspects, we
required an orthogonally C-protected dialkynylated monomer that allows the
regioselective introduction of Br and I substituents and of OH-protecting groups.
We report a short preparation of such an orthogonally C-protected, mono-O-
silylated dialkyne 5, its regioselective C-desilylation and C-halogenation, the cross-
coupling of the resulting monomers, the coupling of the mono-C-desilylated monomers
and dimers to 1-iodo-4-nitrobenzene, and the effect of the 4-nitrophenyl group on the
cross-coupling.
Results and Discussion. ± The bis-C-trimethylsilylated monomer 1 has been
prepared in six steps and with an overall yield of 34% from levoglucosan by a
1
)
Current address: Novartis Crop Protection AG, R-1060.5.36, Postfach, CH-4002 Basel.

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Helvetica Chimica Acta ± Vol. 82 (1999)
sequential alkynylating opening of the oxirane and dioxolane rings of the intermediate
epoxide 2 with (trimethylsilyl) acetylene [1]. For the analogous introduction of the
DOPS-protected2) alkyne 3 [5], we treated the epoxide 2 with the acetylide derived
from 3, BuLi, and AlMe3 (Scheme 1). This yielded 87% of 4 that was readily
transformed into 5 (63% from 2 on a scale of 15 ± 20 g) [6]. The acetal 6 [1], however,
that reacts well with excess TMS-acetylide, proved inert to 3. As the orthogonal
deprotection of 5 proceeded well, we did not persue this reaction.
Scheme 1
TMS ˆ Me3Si, TIPS ˆ (iPr)3Si, DOPS ˆ OCH2CH2C(Me)2Si(Me)2
a) TIPS-DOPS CꢀCH (3), BuLi, AlMe3; 87%. b) 3 equiv. of Me3SiCꢀCH, 3 equiv. of BuLi, 3 equiv. of
AlCl3, toluene; 72%. c) Me3SiCꢀCH, BuLi, AlMe3; 80%. d) 0.25m MeONa, MeOH; 94%. e) NBS,
AgOCOCF3, acetone; 97% from 7. f ) NIS, AgOCOCF3, acetone; 94% from 7. g) 0.01n HCl, EtOH, 458; 97%.
h) BuLi, THF, 788; 97%; or DMSO, 608; >98%. i) as e); 75%. k) as f ); 73%.
Selective desilylation of 5 with MeONa in MeOH3) gave 7 (97%; Scheme 1). Since
bromoalkynes have led to a higher ratio of hetero- to homocoupling products than
iodoalkynes [12], we brominated 7 with N-bromosuccinimide (NBS) in the presence of
AgOCOCF3 [2][13] to give 97% of the bromoalkyne 10. It is remarkable that
bromodesilylation [13] of the propargylic alkynyl group (i.e., the alkynyl group at C(3))
of 5 with excess NBS was not complete after 65 h, while the analogous bromodesi-
lylation of a homopropargylic alkynyl group (i.e., the alkynyl group at C(6)) has been
successful [2], reflecting the higher nucleophilicity of homopropargylic alkynyl ethers
[8]4). To remove the DOPS group of 5, we had to selectively cleave the primary TIPS
ether. This was readily achieved with dilute HCl, and the resulting H-DOPS-protected
2
)
)
DOPS ˆ (1,1-dimethyl-3-oxypropyl)dimethylsilyl.
3
If MeOH contained traces of carbonate, the secondary (i-Pr)3Si (TIPS) group migrated to O C(5) and
O
C(8) to give 8 and 9, respectively, in varying yields. Such silyl migrations in the presence of either base
[7] [8] or acid [9 ± 11] are well precedented.
Presumably, bromodesilylation occurs via a silver acetylide [2].
4
)

Helvetica Chimica Acta ± Vol. 82 (1999)
145
12 (97%) was transformed into 13 with catalytic amounts of BuLi at 788 (97%). The
H-DOPS group was also removed by heating 12 in DMSO for 6 h at 608 (>98%). The
bromoalkyne 14 was obtained in high yields by bromination of either 12 or 13.
In the NMR spectra, the sꢁs of the (CH3)3Si groups appear at 0.17 and the sꢁs of the (CH3)2Si groups at
0.10 ppm; the qꢁs of the (CH3)3Si groups resonate at 0.30 to 0.57 and those of the (CH3)2Si groups at 4.00
to 4.43 ppm. The CH2 groups of the DOPS moiety appear as broad tꢁs at 3.77 and 1.59 ppm. The H CꢀC unit
is evidenced by a d at 2.2 ppm (H C(2')) or at 2.5 ppm (H C(1)) with J(H,H) ꢁ 2.2 Hz and a 13C d at 80 ±
81 ppm.
The 1H-NMR spectra of 5, 7, 12, and 13 in CDCl3 and (D6)DMSO show well-resolved OH signals (Table 1).
There are relevant differences for the HO C(5) and to some extent also for the HO C(8) signals. For the
spectra of 5, 7, 12, and 13 in CDCl3, the J(HO C(5),H C(5)) value of ca. 2.6 ± 2.9 Hz is similar to the
corresponding value for cellobiose [14]. However, while the J in cellobiose reflects the intramolecular H-bond
to O C(5) of the neighbouring unit, HO C(5) of 5, 7, 12, and 13 may form an intramolecular H-bond to
5
O
C(4), as confirmed by the IR band at ca. 3600 cm 1 [15] ). In keeping with this, the J(OH,H) coupling for
HO C(5) increases to ca. 8 Hz in the spectra of (D6)DMSO. This is rationalized by a H-bond to DMSO and by
the restricted rotation of the C(5) OH group, due to the interaction with the bulky C(4) OTIPS substituent.
Indeed, J(HO C(5), H C(5)) ꢁ 5.8 Hz for HO C(5) of the fully deprotected dialkyne corresponding to 12
[4] is as expected for a freely rotating OH group [19].
Table 1. Selected 1H-NMR Chemical Shifts [ppm] and Coupling Constants [Hz] of monomers 5, 7, 12, and 13 in
CDCl3 and (D6)DMSO Solution at 228
In CDCl3
In (D6)DMSO
5
7
12
13
5
7
12
13
HO C(5)
HO C(8)
J(HO C(5),H C(5))
J(HO C(8),H C(8))
J(HO C(8'),H C(8'))
2.35
2.08
2.8
7.6
6.0
2.34
2.00
2.8
7.4
6.0
3.03
2.40
2.8
br.
br.
2.51
2.21
2.9
7.4
6.0
5.00
4.74
8.4
5.0
5.0
5.00
4.73
7.8
5.2
5.2
5.04
4.73
8.1
5.0
5.0
5.15
4.74
8.1
5.6
5.6
The transformation of 5 into 12 is reflected by a downfield shift of 0.7 and 0.3 ppm for HO C(5) and
HO C(8), respectively, presumably due to an intramolecular H-bond from the DOPS moiety of 12 to either
HO C(5) or HO C(8) as confirmed by an IR band at 3438 cm 1. Removal of the H-DOPS group of 12 to 13
6
again shifted the signals of HO C(5) and HO C(8) to higher fields ). MM3* Calculations (Macromodel
V. 6.0) confirmed these observations and showed that H-bond distances are within the expected range.
Chemical-shift values of 5 and 7 ± 15 are summarized in Tables 3 and 4 (see Exper.
Part).
To evaluate the influence of the position of the halo substituent on the cross-
coupling, we compared the propargylic bromoalkynyl ether 10 and the homopropar-
gylic bromoalkynyl ether 14, coupling the former with the alkyne 13 and the latter with
7 (Scheme 2). Coupling 10 with 13 under the optimized conditions resulting from a
study of simple alkynes ([Pd2(dba)3] (dba ˆ dibenzylideneacetone ˆ 1,5-diphenylpen-
ta-1,4-dien-3-one), CuI, LiI, and 1,2,2,6,6-pentamethylpiperidine (PMP) in DMSO
[12]) gave 71% of the heterodimer 16, besides 3% of the homodimer 17 and <1% of
5
)
)
H-Bonds between OH and acetylene groups are known [16 ± 18]; they are rather weak.
The formation of 2,2,3,3-tetramethyl-1-oxasilacyclopentane was characterized by the appearance of two
small t at 3.75 and 1.57 ppm [20]; it was removed under high vacuum concomitantly with DMSO.
6

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Helvetica Chimica Acta ± Vol. 82 (1999)
Scheme 2
TMS ˆ Me3Si, TIPS ˆ (iPr)3Si, DOPS ˆ OCH2CH2C(Me)2Si(Me)2
a) [Pd2(dba)3], CuI, LiI, PMP, DMSO: 16 (71%), 17 (3%), 18 (< 1%), or [Pd2(dba)3], CuI, P(fur)3, Et3N,
DMSO: 16 (79%), 17 (2%), 18 (< 1%). b) [Pd2(dba)3], CuI, LiI, PMP, DMSO: 16 (61%), 17 (4%), 18 (9%);
or [Pd2(dba)3], CuI, P(fur)3, Et3N, DMSO: 16 (64%), 17 (3%), 18 (12%). c) Bu4NF ´ 3 H2O, THF, 08; 92%.
the homodimer 18 (Coupling A, Scheme 2). Coupling of the bromoalkyne 14 with the
alkyne 7, however, yielded 61% of 16, 4% of 17 and 9% of 18 (Coupling B). It is
clearly advantageous to use a propargylic bromoalkynyl ether in the cross-coupling.
However, as compared to previous results [2][12], we considered the cross-coupling
yields insufficient. The results of an optimization are summarized in Table 2.
In agreement with the results of Cadiot and Chodkiewicz [21], we performed the
reaction at 228. Brandsma et al. suggested to proceed at the slightly elevated
temperature resulting from slow addition of the bromoalkyne [22]. As we observed no
heat evolution during the coupling of acetylenosaccharides, we performed the reaction
of 10 and 13 at 508 (Table 2; Coupling A, Entry 2). This led to a faster reaction but
decreased the yield of 16 and gave slightly higher amounts of the homodimer 17. The
results were not affected by the rate of addition of the bromoalkyne.
LiI, expected to reduce homo-coupling [12], had a negligible influence on the
selectivity of the reaction (Entry 3). Use of P(fur)3 [12][23][24] increased the yield of
16 from 71 to 75% (Entry 4); again, higher temperatures were not favourable
(Entry 5). Replacing the bulky PMP by Et3N (Entry 6) shortened the reaction time
and improved the selectivity, in contradistinction to the results with simple alkynes
[12]. Coupling in pyrrolidine (Entry 7) [25][26] induced partial desilylation of 16;
11% of 19 and 43% of 16 being isolated after 10 h. This desilylation was almost
completely suppressed in DMSO/pyrrolidine 5 :1 (Entry 8), but these conditions
showed no advantage over those specified in Entry 6. Coupling in benzene (Entry 9)

Helvetica Chimica Acta ± Vol. 82 (1999)
147
Table 2. Cross-Coupling of Alkynyl-Monomers at 228 (unless stated otherwise)
Entry Conditions
16
17 18 t [h]
Coupling A: Coupling of 10 and 13
1
2
3
4
5
6
7
8
9
[Pd2(dba)3], CuI, DMSO
LiI, PMP
LiI, PMP, 508
PMP
P(fur)3, PMP
P(fur)3, PMP, 508 72
71
64
68
75
3
8
5
2
6
2
8
3
< 1 30
< 1 24
< 1 30
< 1 30
< 1 15
< 1 10
< 1 10
< 1 12
P(fur)3, Et3N
79
[Pd2(dba)3], CuI, pyrrolidine
[Pd2(dba)3], CuI, DMSO
[Pd2(dba)3], CuI, benzene
[Pd(PPh3)4], CuI, DMSO
[Pd(PPh3)4], CuI, benzene
43a)
75
pyrrolidineb)
Et3N
Et3N
55
49
52
12 < 1 20
8
9
10
11
< 1 10
< 1 10
Et3N
Coupling of 11 and 13 12
[Pd2(dba)3], CuI, DMSO
P(fur)3, Et3N
81
3
< 1 10
Coupling B: Coupling of 7 and 14 13
[Pd2(dba)3], CuI, DMSO
LiI, PMP
P(fur)3, Et3N
61
64
4
3
9 30
12 10
14
Coupling of 7 and 15 15
[Pd2(dba)3], CuI, DMSO
P(fur)3, Et3N
61
3
12 10
a) ‡ 11% of 19. b) 16 equiv. of pyrrolidine; ‡ 2% of 19.
decreased the yield of 16 and the selectivity. Using [Pd(PPh3)4] instead of [Pd2(dba)3]
in either DMSO (Entry 10) or benzene (Entry 11) lowered the yields and the ratio
16/17.
Since it is known that the H-DOPS group is removed in situ under cross-coupling
conditons (3 equiv. of Et3N) [2], we also tested the coupling of 10 with the H-DOPs-
protected alkyne 12 under the conditions specified in Entry 6. Neither yield nor
selectivity were affected.
The conditions described in Entry 6 were then applied to the alternative coupling of
7 to 14 (Coupling B, Entry 14). The yield of heterodimer 16 slightly increased, relative
to those described in Entry 13, and so did the amount of the homodimer 18.
The alkynylation of the (alkynyl)(bromo)palladium complex (formed by oxidative
addition of the haloalkyne to Pd0) to give a bis(alkynyl)palladium(II) complex requires
the deprotonation of the terminal alkyne [12]. This deprotonation depends upon the
increased acidity resulting from coordination of the alkyne with Pd and Cu species. The
homopropargylic moiety, being more nucleophilic, will coordinate more readily in
keeping with the regioselective desilylation of homopropargylic C-silyl derivatives with
AgNO2/KCN in MeOH.
To check whether bromo- or iodoalkynes are to be preferred in the cross-coupling,
we prepared the iodoalkynes 11 and 15 (Scheme 1). Surprisingly, coupling 11 to 13
(Table 2, Entry 12) slightly improved the selectivity in favour of the heterodimer 16,
while coupling of iodoalkyne 15 to 7 (Entry 15) led to a decreased selectivity. The
difference between the alternative Couplings A and B is thus even more pronounced
for the more highly reactive iodoalkynes.

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Helvetica Chimica Acta ± Vol. 82 (1999)
In conclusion, the best results were obtained by coupling a propargylic iodoalkynyl
ether and a homopropargylic H-DOPS-protected alkynyl ether in the presence of
[Pd2(dba)3], CuI, P(fur)3, and Et3N in DMSO, yielding 81% of the dimer 16.
The dimer 16 was deprotected with Bu4NF ´ 3 H2O to give 92% of dimer 20
(Scheme 2). Crystallization of 20 from hot MeOH yielded a nano-crystalline material
that refracted polarized light. At ca. 1708, the material started to soften, but it was
difficult to determine a melting region. Differential scanning calorimetry (DSC)
showed a narrow melting peak at 1748. The crystals, however, were not suitable for X-
ray diffraction.
To obtain more readily crystallizable derivatives, we coupled p-nitrophenyl (4-
NO2C6H4) groups to the unprotected acetylene moiety of the monomers 7 and 13
[27][28]. Coupling 13 and 1-iodo-4-nitrobenzene (4-NO2C6H4I) in the presence of
[Pd(PPh3)4] and CuI in Et3N/DMSO yielded 98% of the arylated monomer 21
(Scheme 3); similarly, coupling 7 with 4-NO2C6H4I led in 88% to 24.
Scheme 3
Arˆ 4-NO2C6H4, TMS ˆ Me3Si, TIPS ˆ (iPr)3Si, DOPS ˆ OCH2CH2C(Me)2Si(Me)2
a) 4-NO2C6H4I, [Pd(PPh3)4], CuI, Et3N, DMSO; 98%. b) NBS, AgOCOCF3, acetone; 23 (76%). c) MeONa,
MeOH; 22 (79%). d) NBS, AgOCOCF3, acetone; 23 (97%). e) as a); 88%. f ) 0.01n HCl, EtOH; 90%.
The brominating desilylation of 21, using excess NBS and AgOCOCF3, proceeded
slowly, providing 76% of 23 that was purified by HPLC. C-Desilylation of 21 to 22
(NaOMe/MeOH), followed by bromination gave 23 in about the same yield, but the
product was much more readily purified. O-Desilylation of 24 at the TIPS-DOPS
group yielded 90% of the H-DOPS-protected alkyne 25.
In the 1H-NMR spectrum, H C(3) and H C(6) of the C(1) and C(2') 4-nitrophenylated products,
respectively, are deshielded by 0.2 ± 0.3 ppm (Table 3, see Exper. Part). The chemical shift of the ring C-atoms of
arylated compounds are very similar to those of the non-arylated ones; the 13C-NMR signals of the arylated
ethyne C-atom, however, are shifted upfield by 7 to 12 ppm (Tables 4 and 5, see Exper. Part). The signals of the
terminal or brominated ethyne moiety remained nearly unaffected.
The 4-NO2C6H4 substituent lowered the yields of the Cadiot-Chodkiewicz coupling
([Pd2(dba)3], CuI, LiI, and PMP in DMSO) of the arylated monomers 23 and 25 to the
non-arylated monomers 10 and 13, respectively (Scheme 4). The best yield of an
arylated dimer resulted from coupling 23 to 13; the monoarylated dimer 26 was
obtained in 62%. Use of P(fur)3 and Et3N (instead of LiI and PMP) led only to slightly
better yields of 26. High yields (94%) of 26, however, resulted from coupling of 297) to
7
)
Obtained by treatment of 16 with dilute acid.

Helvetica Chimica Acta ± Vol. 82 (1999)
149
1-iodo-4-nitrobenzene. Coupling of the arylated 23 to the arylated 25 lead to 27 in only
46% yield; this decreased yield is due to the 4-nitrophenyl substituent attached at C(1),
as evidenced by the coupling of 10 and 25, yielding only 40% of 28.
Scheme 4
Arˆ 4-NO2C6H4, TMS ˆ Me3Si, TIPS ˆ (iPr)3Si, DOPS ˆ OCH2CH2C(Me)2Si(Me)2
a) [Pd2(dba)3], CuI, LiI, PMP, DMSO: 26 (62%); or [Pd2(dba)3], CuI, P(fur)3, Et3N, DMSO: 26 (65%). b) as
a); 46%. c) as a); 40%. d) 4-NO2C6H4I, [Pd(PPh3)4], CuI, Et3N, DMSO; 94%.
Complete desilylation (Bu4NF ´ 3 H2O) of the dimer 26 to 30 proceeded in only
29% yield (Scheme 5), while C-desilylation of 26 (NaOMe/MeOH), followed by O-
desilylation (0.3n HCl, 558) yielded 92% of 30. O-Desilylation of the diarylated 27
Scheme 5
Arˆ 4-NO2C6H4, TMS ˆ Me3Si, TIPS ˆ (iPr)3Si, DOPS ˆ OCH2CH2C(Me)2Si(Me)2
a) Bu4NF ´ 3 H2O, THF, 08; 29%. b) MeONa, MeOH, c) 0.3n HCl/MeOH, 558; 92%. d) as c); 97%. e) 0.01n
HCl, EtOH. f ) Et3N, MeOH. g) as c); 75% from 33.

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Helvetica Chimica Acta ± Vol. 82 (1999)
(0.3n HCl/MeOH, 558) yielded 97% of 32. Selective O-desilylation at the protected
primary hydroxy group of 28 to 33 followed by treatment with Et3N in MeOH gave 34
that was fully deprotected (0.3n HCl at 558) to 35 (75%).
The deprotected arylated dimers are white to beige powders that refract polarized
light. However, no crystals suitable for X-ray diffraction could be obtained.
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. See [1]. The molecular ions of the oligomers with molecular weight >1000 were detected by
MALDI-TOF mass spectrometry with either a-cyano-4-hydroxycinnamic acid (CCA, 0.05 ± 0.1m in MeCN/
EtOH/H2O) or indole-3-acetic acid (IAA, 0.05m in THF).
[3-(Ethynyldimethylsilyl)-3-methylbutoxy]triisopropylsilane (3). At 08, a soln. of 3-{dimethyl[(trimethyl-
silyl)ethynyl]silyl}-3-methylbutan-1-ol [2] (7.29 g, 30.0 mmol) and 2,6-dimethylpyridine (8.7 ml, 75.0 mmol) in
dry CH2Cl2 (100 ml) was treated dropwise with (i-Pr)3SiOTf (TIPSOTf; 10.5 ml, 39.1 mmol), stirred for 2 h, and
treated with H2O (40 ml). Usual workup (CH2Cl2, H2O, sat. NaCl) and FC (hexane) gave {1,1-dimethyl-3-
[(triisopropylsilyl)oxy]propyl}dimethyl[(trimethylsilyl)ethynyl]silane (10.68 g, 96%). Transparent oil. Rf (hex-
ane) 0.28. IR (CHCl3): 2960s, 2944s, 2892m, 2866s, 1464m, 1410w, 1384w, 1365w, 1252s(br.), 1093m, 1069m,
1014w, 997w, 919w, 882m, 846s, 840s, 825s, 818s(br.). 1H-NMR (300 MHz, CDCl3): 3.81 (t, J ˆ 7.8, 2H C(3));
1.63 (t, J ˆ 7.8, 2H C(2)); 1.10 ± 1.03 (m, (Me2CH)3Si); 0.98 (s, Me2C); 0.16 (s, Me3Si); 0.12 (s, Me2Si).
13C-NMR (75 MHz, CDCl3): 115.11, 112.22 (2s, CꢀC); 60.58 (t, C(3)); 42.20 (t, C(2)); 23.61 (q, Me2C); 18.69
‡
(s, Me2C); 18.26 (q, 3 Me2CH); 12.22 (d, 3 Me2CH); 0.05 (q, Me3Si); 4.07 (q, Me2Si). EI-MS: 398 (< 1, M ),
359(7), 356(13), 355(40), 287(14), 286(34), 285(100), 244(15), 243(59), 215(54), 203(10), 202(15),
‡
‡
‡
201(65), 157(16, TIPS ), 155(38), 145(7, DOPS ), 133(12), 73 (57, Me3Si ), 59 (23). Anal. calc. for
C21H46OSi3 (398.85): C 63.24, H 11.62; found: C 63.12, H 11.49.
At 228, a soln. of {1,1-Dimethyl-3-[(triisopropylsilyl)oxy]propyl}dimethyl[(trimethylsilyl)ethynyl]silane
(14.58 g, 36.6 mmol) in dry, freshly distilled MeOH (240 ml) was treated with freshly prepared MeONa (0.25m in
MeOH, 30 ml) and stirred for 3 h. After addition of Amberlite IR-120, the mixture was filtered and the filtrate
was evaporated under reduced pressure. Destillation (0.4 mbar, 548) gave 3 (11.76 g, 98%). Transparent oil. Rf
(hexane) 0.27. IR (CHCl3): 3287m, 2944s, 2891s, 2866s, 2727w, 1464s, 1412w, 1384m, 1365w, 1255s (br.), 1162w,
1
1094s, 1070s, 1014m, 997m, 966w, 936w, 919w, 883s, 841s, 824s(br.), 571w, 508w. H-NMR (300 MHz, CDCl3):
3.82 (t, J ꢁ 7.8, 2 H C(3)); 2.37 (s, HCꢀC); 1.64 (t, J ꢁ 7.8, 2 H C(2)); 1.07 ± 1.03 (m, (Me2CH)3Si); 1.00
(s, Me2C); 0.16 (s, Me2Si). 13C-NMR (50 MHz, CDCl3): 94.37 (d, HCꢀC); 88.79 (s, HCꢀC); 60.53 (t, C(3));
42.02 (t, C(2)); 23.54 (q, Me2C); 18.61 (s, Me2C); 18.24 (q, 3 Me2CH); 12.18 (d, 3 Me2CH); 4.18 (q, Me2Si).
‡
CI-MS: 327 (27, [M ‡ 1] ), 302(13), 301(50), 293(67), 231(24), 215(28), 214(20), 213(82), 185(44), 157
‡
‡
(47, TIPS ), 145 (28, DOPS ), 142(45), 49(100).
1,6-Anhydro-4-deoxy-4-C-{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-2-O-(tri-
isopropylsilyl)-b-d-glucopyranose (4). At 158, a soln. of 3 (16.9 g, 51.7 mmol) in dry toluene (30 ml) was
treated dropwise with BuLi (21 ml, 2.3m in hexane, 51.7 mmol), warmed to 208, stirred for 30 min, cooled to
158, treated dropwise with a soln. of Me3Al (26 ml, 2m in toluene, 51.7 mmol), and stirred at 208 for 60 min
( ! white precipitate). The suspension was heated to 758 and treated with a soln. of 2 [1] (10.4 g, 34.5 mmol) in
toluene (30 ml) via a double-ended needle. After 2 h at 758, the mixture was cooled to 08 and slowly treated with
a sat. NH4Cl soln. (5 ml). Filtration over Celite, usual workup (AcOEt, H2O), and FC (AcOEt/hexane 1 : 15)
gave 4 (15.3 g, 71%). Transparent syrup. Rf (toluene/AcOEt 15 : 1) 0.13. [a]D25
ˆ
53.05 (c ˆ 1.9, CHCl3). IR
(CHCl3): 3424m(br.), 3007s, 2945s, 2867s, 2839m, 2177w, 1603w, 1464m, 1384w, 1334w, 1248w, 1101m, 1016s,
919w, 883m, 868w, 838w, 658w(br.). 1H-NMR (500 MHz, CDCl3): 5.40 (br. s, H C(1)); 4.61 (br. d, J ˆ 4.8,
H
C(5)); 3.94 (d, J ˆ 7.3, Hendo C(6)); 3.81 ± 3.78 (m, H C(3), CH2CH2OSi); 3.67 (dd, J ˆ 7.3, 4.8,
Hexo C(6)); 3.61 (dd, J ˆ 3.0, 1.4, H C(2)); 2.65 (dd, J ˆ 3.9, 1.7, H C(4)); 2.35 (d, J ˆ 6.7, HO C(3)); 1.62
(t, J ˆ 7.3, CH2CH2OSi); 1.13 ± 1.06 (m, 2 (Me2CH)3Si); 0.97 (s, Me2C); 0.10 (s, Me2Si). 13C-NMR (75 MHz,
CDCl3): 106.11 (s, C(1')); 103.40 (d, C(1)); 84.84 (s, C(2')); 75.47 (d, C(5)); 73.42 (d, C(2)); 73.33 (d, C(3));
68.16 (t, C(6)); 60.28 (t, CH2CH2OSi); 41.66 (t, CH2CH2OSi); 38.35 (d, C(4)); 23.41 (q, Me2C); 18.63 (s, Me2C);
18.07 (q, 3 Me2CH); 18.03 (q, 3 Me2CH); 12.20 (d, 3 Me2CH); 12.02 (d, 3 Me2CH); 4.15 (q, Me2Si). CI-MS:

Helvetica Chimica Acta ± Vol. 82 (1999)
151
‡
‡
‡
645 (2, [M ‡ NH4] ), 628 (4, [M ‡ 1] ), 627 (49, M ), 453(16), 409(16), 303(16), 302(46), 301 (100, TIPS-
‡
‡
‡
DOPS ), 248(16), 233(26), 205(18), 157 (7, TIPS ), 145 (5, DOPS ), 132(16). Anal. calc. for C33H66O5Si3
(627.14): C 63.20, H 10.61; found: C 63.11, H 10.51.
3,7-Anhydro-1,2,6-trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-4-
O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (5). At 158, a soln. of (trimethylsilyl)-
acetylene (7.5 ml, 55.2 mmol) in dry toluene (50 ml) was treated dropwise with BuLi (23.5 ml, 2.3m in hexane,
55.2 mmol), stirred for 30 min at 218, diluted with THF (2 ml) and added to a 158 cold, mechanically stirred
suspension of AlCl3 (7.27 g, 55.2 mmol) in dry toluene (40 ml) via a double-ended needle. Upon stirring at 218
for 45 min, a white precipitate was formed. The mixture was heated to 908 (bath temp.) and treated dropwise
with a soln. of 4 (11.39 g, 18.2 mmol) in dry toluene (80 ml) leading to dissolution of the precipitate. After
stirring for 18 h at 908, the soln. was cooled to 08 and treated with a sat. NH4Cl soln. (10 ml). Usual workup
(AcOEt, H2O) and FC (AcOEt/hexane 1 : 15) gave 5 (9.77 g, 74%). White solid. Rf (toluene/hexane 15 : 1) 0.22.
M.p. 828. [a]2D5
ˆ
23.2 (c ˆ 1.2, CHCl3). IR (CHCl3): 3595w, 3427w, 3008m, 2945s, 2892s, 2867s, 2174w, 1522w,
1464m, 1384w, 1365w, 1349w, 1290w, 1252m(br.), 1143m, 1101s, 1071m, 1048m, 1014m, 991m, 919w, 883s, 845s,
824s(br.), 604w, 571w, 532w, 524w, 506w. 1H-NMR (500 MHz, CDCl3): 3.95 (d, J ˆ 9.3, H C(3)); 3.93
(ddd, J ˆ 12.0, 7.6, 2.7, H C(8)); 3.77 (t, J ˆ 7.7, CH2CH2OSi); 3.73 (dt, J ꢁ 12.0, 6.1, H' C(8)); 3.63 (dd, J ˆ
9.3, 8.3, H C(4)); 3.49 (ddd, J ꢁ 10.3, 8.3, 2.8, H C(5)); 3.43 (ddd, J ꢁ 10.3, 6.1, 2.7, H C(7)); 2.54 (t, J ˆ 10.3,
H
C(6)); 2.35 (d, J ˆ 2.8, HO C(5)); 2.08 (dd, J ꢁ 7.6, 6.0, HO C(8)); 1.60 (t, J ˆ 7.7, CH2CH2OSi); 1.24 ±
1.06 (m, 2 (Me2CH)3Si); 0.96 (s, Me2C); 0.16 (s, Me3Si); 0.11 (s, Me2Si). 1H-NMR (300 MHz, (D6)DMSO):
5.00 (d, J ˆ 8.4, HO C(5)); 4.74 (t, J ˆ 5.0, HO C(8)); 3.87 (d, J ˆ 9.0, H C(3)); 3.72 (t, J ˆ 7.7, CH2CH2O-
Si); 3.70 ± 3.64 (m, H C(8)); 3.44 (dt, J ˆ 11.8, 5.6, H' C(8)); 3.37 ± 3.17 (m, H C(4), H C(5), H C(7));
2.47 ± 2.43 (m, H C(6)); 1.51 (t, J ˆ 7.8, CH2CH2OSi); 1.21 ± 1.02 (m, (Me2CH)3Si); 0.91 (s, Me2C); 0.09
(s, Me3Si); 0.04 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 102.58 (s); 102.34 (s); 91.10 (s); 88.28 (s); 78.91 (d);
76.89 (d); 75.05 (d); 71.97 (d); 63.70 (t); 60.16 (t); 41.64 (t); 39.12 (d); 23.38 (2q); 18.52 (s); 18.36 (6q); 18.08
‡
‡
(6q); 13.09 (3d); 12.01 (3d); 0.37 (3q); 4.12 (2q). MS: 726 (2, [M ‡ 1] ), 725 (4, M ), 507(6), 303(14),
‡
‡
‡
302(40), 301 (100, TIPS-DOPS ), 297(12), 231(13), 205(18), 157 (6, TIPS ), 145 (2, DOPS ), 73 (10,
‡
Me3Si ). Anal. calc. for C38H76O5Si4 (725.36): C 62.92, H 10.56; found: C 62.77, H 10.47.
3,7-Anhydro-1,2,6-trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-4-
O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (7). At 228, a soln. of 5 (2.73 g. 3.77 mmol) in dry, freshly
distilled MeOH (100 ml) was treated with freshly prepared MeONa (0.25m in MeOH, 5 ml) and stirred for 3.5 h.
After addition of Amberlite IR-120, the mixture was filtered and the filtrate evaporated under reduced pressure
to give 7 (2.31 g, 94%). Transparent syrup. Rf (AcOEt/hexane 3 :17) 0.24. [a]D25
ˆ
24.6 (c ˆ 0.54, CHCl3). IR
(CHCl3): 3592w, 3429w(br.), 3306w, 3008w, 2945s, 2892m, 2867s, 2171w, 1602w, 1464m, 1384w, 1366w,
1256w(br.), 1144m, 1097s, 1047m, 1014w, 963w, 932w, 883w, 840w, 823m(br.), 652w, 603w, 540w. 1H-NMR
(500 MHz, CDCl3): 3.95 (dd, J ˆ 9.3, 2.2, H C(3)); 3.93 (ddd, J ˆ 12.0, 7.4, 2.6, H C(8)); 3.77 (t, J ˆ 7.7,
CH2CH2OSi); 3.72 (dt, J ˆ 12.0, 6.0, H' C(8)); 3.66 (dd, J ˆ 9.3, 8.3, H C(4)); 3.51 (ddd, J ˆ 10.3, 8.3, 2.8,
H
C(5)); 3.45 (ddd, J ˆ 10.3, 6.0, 2.6, H C(7)); 2.56 (t, J ˆ 10.3, H C(6)); 2.47 (d, J ˆ 2.2, H C(1)); 2.39
(d, J ˆ 2.8, HO C(5)); 2.00 (dd, J ˆ 7.4, 6.1, HO C(8)); 1.60 (t, J ˆ 7.7, CH2CH2OSi); 1.23 ± 1.05
(m, 2 (Me2CH)3Si); 0.97 (s, Me2C); 0.12 (s, Me2Si). 1H-NMR (300 MHz, (D6)DMSO): 5.00 (d, J ˆ 7.8,
HO C(5)); 4.73 (t, J ˆ 5.2, HO C(8)); 3.84 (dd, J ˆ 9.0, 2.2, H C(3)); 3.73 (t, J ˆ 7.7, CH2CH2OSi); 3.70 ±
3.64 (m, H C(8)); 3.44 (dt, J ˆ 11.8, 5.6, H' C(8)); 3.37 (d, J ˆ 2.2, H C(1)); 3.34 ± 3.17 (m, H C(4),
H
C(5), H C(7)); 2.47 ± 2.43 (m, H C(6)); 1.51 (t, J ˆ 7.8, CH2CH2OSi); 1.21 ± 1.02 (m, (Me2CH)3Si); 0.90
(s, Me2C); 0.04 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 102.44 (s); 88.43 (s); 81.04 (d); 79.02 (d); 76.78 (d);
75.02 (d); 74.54 (s); 71.38 (d); 63.89 (t); 60.14 (t); 41.83 (t); 39.14 (d); 23.34 (2q); 18.52 (s); 18.36 (6q); 18.08
‡
‡
(6q); 13.02 (3d); 12.01 (3d); 4.12 (2q). CI-MS: 654 (13, [M ‡ 1] ), 653 (24, M ), 609(10), 435(9), 305(18),
‡
‡
‡
303(13), 302(37), 301 (100, TIPS-DOPS ), 248(11), 231(14), 205(12), 157 (5, TIPS ), 145 (3, DOPS ), 111
(6). Anal. calc. for C35H68O5Si3 (653.18): C 64.36, H 10.49; found: C 64.35, H 10.43.
Isomerization of 7: Mixture of 7, 3,7-Anhydro-1,2,6-trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropyl-
silyl)oxy] propyl}silyl}ethynyl}-5-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (8), and 3,7-Anhydro-1,2,6-
trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-8-O-(triisopropylsilyl)-d-
glycero-d-gulo-oct-1-ynitol (9). In the presence of traces of carbonate, 7 as well as the two isomers 8 and 9 have
been isolated in varying yields.
Data of 8: Rf (AcOEt/hexane 3 :17) 0.08. [a]D25
ˆ
23.9 (c ˆ 0.49, CHCl3). IR (CHCl3): 3598m, 3306m,
2945s, 2892s, 2172m, 2122w, 1711w, 1464s, 1384m, 1365m, 1298w, 1252s(br.), 1141s, 1085s, 1014s, 997s, 919w, 883s,
818s, 582s, 509w. 1H-NMR (500 MHz, CDCl3): 3.97 (dd, J ˆ 9.7, 2.2, H C(3)); 3.96 (ddd, J ˆ 12.0, 7.3, 2.6,
H
C(8)); 3.78 (dd, J ˆ 10.3, 8.3, H C(5)); 3.77 (t, J ˆ 7.7, CH2CH2OSi); 3.75 (dt, J ꢁ 12.0, 6.0, H' C(8)); 3.47

152
Helvetica Chimica Acta ± Vol. 82 (1999)
(ddd, J ꢁ 10.5, 5.8, 2.6, H C(7)); 3.40 (ddd, J ˆ 9.7, 8.3, 3.1, H C(4)); 2.60 (t, J ˆ 10.3, H C(6)); 2.57 (d, J ˆ
2.2, H C(1)); 2.31 (d, J ˆ 2.8, HO C(4)); 2.03 (dd, J ˆ 7.3, 6.3, HO C(8)); 1.60 (t, J ˆ 7.7, CH2CH2OSi);
1.23 ± 1.05 (m, 2 (Me2CH)3Si); 0.96 (s, Me2C); 0.10 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 104.25 (s); 87.67
(s); 80.09 (d); 79.97 (d); 76.61 (d); 75.24 (d); 74.82 (s); 70.55 (d); 63.69 (t); 60.10 (t); 41.40 (t); 39.68 (d); 23.26
‡
(2q); 18.53 (s); 18.43 (6q), 18.08 (6q); 13.06 (3d); 12.00 (3d); 4.32 (q); 4.40 (q). CI-MS: 654 (13, [M ‡ 1] ),
‡
‡
653 (24, M ), 609(10), 435(9), 305(18), 303(13), 302(37), 301 (100, TIPS-DOPS ), 248(11), 231(14),
‡
‡
205(12), 157 (5, TIPS ), 145 (3, DOPS ), 111 (6). Anal. calc. for C35H68O5Si3 (653.18): C 64.36, H 10.49;
found: C 64.41, H 10.39.
Data of 9: Rf (AcOEt/hexane 3 :17) 0.22. [a]D25
ˆ
23.1 (c ˆ 0.47, CHCl3). IR (CHCl3): 3608m, 3306m,
3008m, 2945s, 2892s, 2867s, 2172w, 1734m, 1464m, 1386w, 1365w, 1260s(br.), 1133s, 1090s, 1014s, 883s, 818s, 653w.
1H-NMR (300 MHz, CDCl3): 4.50 (dd, J ˆ 12.1, 1.8, H C(8)); 4.21 (dd, J ˆ 12.1, 6.0, H' C(8)); 3.94 (dd, J ˆ
9.7, 2.2, H C(3)); 3.773 (ddd, J ꢁ 10.1, 8.4, 2.1, H C(5)); 3.767 (t, J ꢁ 7.6, CH2CH2OSi); 3.60 (ddd, J ˆ 10.6, 6.0,
1.8, H C(7)); 3.42 (ddd, J ꢁ 9.6, 8.4, 3.2, H C(4)); 2.60 (t, J ˆ 10.5, H C(6)); 2.57 (d, J ˆ 2.1, HO C(5)); 2.56
(d, J ˆ 2.2, H C(1)); 2.33 (d, J ˆ 2.8, HO C(4)); 1.58 (t, J ꢁ 7.5, CH2CH2OSi); 1.25 ± 1.05 (m, 2 (Me2CH)3Si);
0.96 (s, Me2C); 0.09 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 103.80 (s); 88.07 (s); 79.93 (d); 77.65 (d); 76.59 (d);
75.06 (d); 74.94 (s); 70.68 (d); 64.88 (t); 60.06 (t); 41.24 (t); 39.93 (d); 23.16 (2q); 18.52 (s); 18.39 (6q); 18.09
‡
‡
(6q); 13.05 (3d); 12.00 (3d); 4.38 (q); 4.43 (q). CI-MS: 654 (6, [M ‡ 1] ), 653 (17, M ), 652(35), 651(66),
‡
447(11), 451(20), 347(17), 303(11), 302(27), 301 (100, TIPS-DOPS ), 248(29), 247(27), 231(27), 157 (11,
TIPS ), 145 (7, DOPS ), 117(16), 75(10). Anal. calc. for C35H68O5Si3 (653.18): C 64.36, H 10.49; found:
C 64.40, H 10.41.
‡
‡
3,7-Anhydro-1-C-bromo-1,2,6-trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}-
ethynyl}-4-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (10). A soln. of 7 (5.98 g, 9.07 mmol) and NBS
(1.70 g, 9.53 mmol) in dry acetone (300 ml) was treated with AgOCOCF3 (60.1 mg, 0.27 mmol) and stirred in
the dark (Al foil) at 218 for 1 h. After completion, the mixture was worked up normally (Et2O, H2O). FC
(AcOEt/hexane 3 :47) gave 10 (6.47 g, 97%). Transparent syrup. Rf (AcOEt/hexane 1:4) 0.59. [a]D25
ˆ
27.6
(c ˆ 0.5, CHCl3). IR (CHCl3): 3604m, 3008m, 2945s, 2892m, 2867s, 2172w, 1605w, 1464m, 1384w, 1366w, 1253m,
1002s, 1047m, 997m, 932w, 883m, 840m, 824m(br.), 654m, 602w, 504w. 1H-NMR (500 MHz, CDCl3): 3.97
(d, J ˆ 9.3, H C(3)); 3.93 (ddd, J ˆ 12.0, 7.4, 2.6, H C(8)); 3.78 (t, J ꢁ 7.7, CH2CH2OSi); 3.72 (dt, J ˆ 12.0, 6.0,
H' C(8)); 3.64 (dd, J ˆ 9.3, 8.4, H C(4)); 3.50 (ddd, J ꢁ 10.4, 8.4, 2.8, H C(5)); 3.44 (ddd, J ˆ 10.3, 5.9, 2.6,
H
C(7)); 2.55 (t, J ˆ 10.3, H C(6)); 2.35 (d, J ˆ 2.8, HO C(5)); 1.99 (dd, J ˆ 7.4, 6.1, HO C(8)); 1.60 (t, J ꢁ
7.7, CH2CH2OSi); 1.26 ± 1.04 (m, 2 (Me2CH)3Si); 0.96 (s, Me2C); 0.11 (s, Me2Si). 13C-NMR (75 MHz, CDCl3):
102.40 (s); 88.42 (s); 78.99 (d); 76.89 (s); 76.70 (d); 75.16 (d); 72.26 (d); 63.63 (t); 60.15 (t); 47.21 (s); 41.64 (t);
39.07 (d); 23.35 (2q); 18.37 (s); 18.26 ± 18.21 (6q); 18.09 (6q); 12.94 (3d); 12.01 (3d); 4.12 (2q). CI-MS:
‡
‡
‡
734(2), 733(5), 732 (2, [M ‡ 1] ), 731 (4, M ), 303(14), 302(35), 301 (100, TIPS-DOPS ), 231(11),
‡
‡
205(20), 174(6), 157 (7, TIPS ), 148(6), 145 (4, DOPS ). Anal. calc. for C35H67BrO5Si3 (732.07): C 57.42,
H 9.22; found: C 57.45, H 9.26.
3,7-Anhydro-1,2,6-trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-1-
C-iodo-4-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (11). A soln. of 7 (2.1 g, 3.22 mmol) and NIS
(0.798 g, 3.55 mmol) in dry acetone (110 ml) was treated with AgOCOCF3 (36.0 mg, 0.161 mmol) and stirred in
the dark (Al foil) at 218 for 1 h. After completion, the mixture was worked up normally (Et2O, H2O). FC
(AcOEt/hexane 1 :9) gave 11 (2.35 g, 94%). White foam. Rf (AcOEt/hexane 1:3) 0.48. M.p. 101.5 ± 102.58.
[a]2D5
ˆ
21.8 (c ˆ 0.6, CHCl3). IR (CHCl3): 3593w, 2945s, 2892s, 2867s, 2172w, 1602w, 1464m, 1384w, 1365w,
1291w, 1261s, 1142m, 1099s, 1014s, 919w, 883m, 818m, 601w, 524w, 508w. 1H-NMR (500 MHz, CDCl3): 4.08
(d, J ˆ 9.3, H C(3)); 3.94 (m, H C(8)); 3.77 (t, J ˆ 7.7, CH2CH2OSi); 3.72 (td, J ˆ 12.0, 6.0, H' C(8)); 3.64
(dd, J ˆ 9.3, 8.4, H C(4)); 3.50 (ddd, J ꢁ 10.4, 8.4, 2.7, H C(5)); 3.43 (ddd, J ˆ 10.4, 6.0, 2.7, H C(7)); 2.56
(t, J ꢁ 10.4, H C(6)); 2.36 (d, J ˆ 2.7, HO C(5)); 2.01 (br. t, J ꢁ 6.5, HO C(8)); 1.60 (t, J ˆ 7.7, CH2CH2OSi);
1.28 ± 1.06 (m, 2 (Me2CH)3Si); 0.96 (s, Me2C); 0.11 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 102.42 (s); 91.37
(s); 88.38 (s); 78.98 (d); 76.73 (d); 75.34 (d); 72.79 (d); 63.63 (t); 60.15 (t); 41.64 (t); 39.04 (d); 23.37 (2q); 18.52
‡
(s); 18.31 (6q); 18.09 (6q); 13.02 (3d); 12.01 (3d); 5.00 (s); 1.04 (s); 4.12 (2q). CI-MS: 779 (1, M ), 735(1),
653(3), 453(3), 303(10), 302(25), 301 (100, TIPS-DOPS ), 231(15), 205(22), 173(6), 157 (8, TIPS ), 145
(3, DOPS ), 131(10), 103(7), 49(12). Anal. calc. for C35H67IO5Si3 (779.07): C 53.96, H 8.67, I 16.29; found:
‡
‡
‡
C 53.93, H 8.45, I 16.06.
3,7-Anhydro-1,2,6-trideoxy-6-C-{[(3-hydroxy-1,1-dimethylpropyl)dimethylsilyl]ethynyl}-4-O-(triisopropyl-
silyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (12). A soln. of 5 (109.8 mg, 0.151 mmol) in EtOH
(2.5 ml) was treated with 0.1n HCl (0.3 ml) and stirred at 508 for 5.5 h. After evaporation, FC (AcOEt/hexane
3 :17 ! 1 : 3) gave 12 (83.6 mg, 97%). White foam. Rf (AcOEt/hexane 1 : 3) 0.17. M.p. 129 ± 1308. [a]D25
ˆ
29.8

Helvetica Chimica Acta ± Vol. 82 (1999)
153
(c ˆ 1.72, CHCl3). IR (CHCl3): 3597w, 3438w(br.), 3008m, 2946s, 2892s, 2866s, 2174m, 1602w, 1464m, 1386m,
1364m, 1349m, 1291m, 1252s, 1144s, 1102s, 1071s, 991s, 918w, 884s, 845s, 822m, 655w. 1H-NMR (300 MHz,
CDCl3): 3.95 (d, J ˆ 9.2,
H
C(3)); 3.96 ± 3.92 (m, H C(8)); 3.77 (t, J ˆ 7.2, CH2OH); 3.78 ± 3.68
C(4)); 3.55 ± 3.50 (m, H C(5)); 3.43 (ddd, J ˆ 10.3, 6.2, 2.8,
C(6)); 2.40 (br. s, HO C(8)); 1.83
(m, H' C(8)); 3.61 (dd, J ˆ 9.3, 8.4,
H
H
C(7)); 3.03 (d, J ˆ 2.8, HO C(5)); 2.53 (t, J ˆ 10.3,
H
(br. s, CH2CH2OH); 1.60 (t, J ˆ 7.2, CH2CH2OH); 1.19 ± 1.08 (m, (Me2CH)3Si); 0.95 (s, Me2C); 0.16 (s, Me3Si);
0.11 (s, Me2Si). 1H-NMR (300 MHz, (D6)DMSO): 5.04 (d, J ˆ 8.1, HO C(5)); 4.73 (t, J ˆ 5.0, HO C(8));
4.26 (t, J ˆ 5.0, CH2CH2OH); 3.92 (d, J ˆ 9.3, H C(3)); 3.74 ± 3.61 (m, H C(8)); 3.49 ± 3.43 (m, H' C(8),
CH2CH2OH); 3.36 ± 3.18 (m, H C(4),
H
C(5),
H
C(7)); 2.51 ± 2.48 (m, H C(6)); 1.42 (t, J ˆ 7.8,
CH2CH2OH); 1.21 ± 1.02 (m, (Me2CH)3Si); 0.89 (s, Me2C); 0.09 (s, Me3Si); 0.04 (s, Me2Si). 13C-NMR
(75 MHz, CDCl3): 103.40 (s); 102.40 (s); 91.06 (s); 87.99 (s); 79.02 (d); 76.81 (d); 75.03 (d); 71.97 (d); 63.65
(t); 59.93 (t); 42.83 (t); 39.06 (d); 23.94 (2q); 18.87 (s); 18.23 (6q); 12.90 (3d); 0.56 (3q); 4.17 (2q). CI-MS:
‡
569 (1, M ), 444(10), 443(25), 442(71), 425(53), 322(20), 321(69), 255(18), 233(15), 148(25), 146(26), 145
‡
(100, DOPS ), 144(11), 129(67), 103(25), 75(97), 73(37), 48(14). Anal. calc. for C29H56O5Si3 (569.02):
C 61.21, H 9.92; found: C 61.25, H 10.43.
3,7-Anhydro-1,2,6-trideoxy-6-C-ethynyl-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-
ynitol (13). As described in [1]; crystallization from Et2O/hexane instead of FC. Data: see [1]. 1H-NMR
(300 MHz, (D6)DMSO): 5.15 (d, J ˆ 8.1, HO C(5)); 4.74 (t, J ˆ 5.6, HO C(8)); 3.92 (d, J ˆ 9.3, H C(3));
3.63 (ddd, J ˆ 11.4, 5.0, 0.8, H C(8)); 3.45 (dt, J ˆ 11.5, 5.3, H' C(8)); 3.36 ± 3.18 (m, H C(4), H C(5),
H
C(7)); 2.96 (d, J ˆ 2.2, H C(2')); 2.37 (td, J ˆ 10.3, 2.5, H C(6)); 1.21 ± 1.02 (m, (Me2CH)3Si); 0.09
(s, Me3Si).
3,7-Anhydro-1,2,6-trideoxy-6-C-(bromoethynyl)-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-
gulo-oct-1-ynitol (14). A soln. of 13 (322.4 mg, 0.759 mmol) and NBS (141.9 mg, 0.797 mmol) in dry acetone
(40 ml) was treated with AgOCOCF3 (8.4 mg, 0.0380 mmol) and stirred in the dark (Al foil) at 218 for 6 h. After
completion, the mixture was worked up normally (Et2O, H2O). FC (AcOEt/hexane 1:9) gave 14 (0.29 g, 75%).
White foam. Rf (AcOEt/hexane 1:2) 0.58. M.p. 658. [a]D25
ˆ
33.3 (c ˆ 0.5, CHCl3). IR (CHCl3): 3579m, 2990s,
2945m, 2864w, 2172w, 1588m, 1490m, 1462m, 1351s(br.), 1139m, 1117m, 978s, 901w, 887m, 862m, 840s(br.),
643s(br.), 601m. 1H-NMR (300 MHz, CDCl3): 3.97 (d, J ˆ 9.1, H C(3)); 3.96 ± 3.93 (m, H C(8)); 3.73 (dt, J ˆ
12.0, 6.0, H' C(8)); 3.63 (dd, J ꢁ 9.0, 8.3, H C(4)); 3.54 (ddd, J ˆ 10.3, 8.3, 3.0, H C(5)); 3.46 (ddd, J ˆ 10.3,
5.7, 2.5, H C(7)); 2.59 (t, J ˆ 10.3, H C(6)); 2.44 (d, J ˆ 3.0, HO C(5)); 2.05 (dd, J ˆ 7.4, 6.2, HO C(8));
1.27 ± 1.09 (m, (Me2CH)3Si); 0.18 (s, Me3Si). 13C-NMR (75 MHz, CDCl3): 101.82 (s); 91.02 (s); 78.44 (d); 76.47
(d); 75.83 (s); 74.91 (d); 71.01 (d); 63.17 (t); 43.36 (s); 38.33 (d); 18.06 (6q); 12.77 (3d); 0.68 (3q). CI-MS:
‡
‡
523(34), 521 (32, [M ‡ NH4] ), 505(10), 503 (9, M ), 442(25), 426(17), 401(33), 399(32), 321(40),
‡
‡
148(89), 157 (24, TIPS ), 131(87), 103(61), 73 (100, Me3Si ). Anal. calc. for C22H39BrO4Si2 (503.62): C 52.47,
H 7.81; found: C 52.55, H 7.69.
3,7-Anhydro-1,2,6-trideoxy-6-C-(iodoethynyl)-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-
oct-1-ynitol (15). A soln. of 13 (126.9 mg, 0.299 mmol) and NIS (73.9 mg, 0.329 mmol) in dry acetone (3 ml) was
treated with AgOCOCF3 (3.3 mg, 0.0149 mmol) and stirred in the dark (Al foil) at 218 for 3 h. After
completion, the mixture was worked up normally (Et2O, H2O). FC (AcOEt/hexane 1:9) gave 15 (120.2 mg,
73%). White foam. Rf (AcOEt/hexane 1 :2) 0.57. [a]D25
ˆ
32.8 (c ˆ 0.5, CHCl3). IR (CHCl3): 3601s, 3008s,
2946s, 2867s, 2399m, 2180m, 1602m, 1520w, 1464m, 1391m, 1366m, 1349m, 1291m, 1265m, 1252s, 1144s, 1104s,
1072s, 1047s, 1017m, 991m, 931w, 884s, 846s, 653m, 638w. 1H-NMR (300 MHz, CDCl3): 3.95 (d, J ˆ 9.0,
H
H
H
C(3)); 3.93 (ddd, J ˆ 11.8, 7.2, 2.5, H C(8)); 3.72 (td, J ˆ 11.8, 5.9, H' C(8)); 3.61 (dd, J ˆ 9.0, 8.4,
C(4)); 3.53 (ddd, J ˆ 10.3, 8.1, 3.1, H C(5)); 3.45 (ddd, J ˆ 10.3, 5.9, 2.8, H C(7)); 2.70 (t, J ˆ 10.3,
C(6)); 2.49 (d, J ˆ 2.8, HO C(5)); 2.12 (br. t, J ꢁ 6.7, 6.2, HO C(8)); 1.25 ± 1.10 (m, (Me2CH)3Si); 0.16
(s, Me3Si). 13C-NMR (75 MHz, CDCl3): 102.16 (s); 91.34 (s); 90.16 (s); 78.91 (d); 76.91 (d); 75.19 (d); 71.91 (d);
‡
63.46 (t); 39.55 (d); 18.23 (6q); 14.01 (s); 12.92 (3d); 0.55 (3q). CI-MS: 568 (15, [M ‡ NH4] ), 551 (9, [M ‡
‡
‡
1] ), 447(29), 444(9), 443(12), 442(37), 425(35), 321(74), 297(45), 255(57), 157 (23, TIPS ), 131(96),
103(60), 73(100).
Coupling of 10 with 13. A soln. of 10 (3.45 g, 4.71 mmol), 13 (2.00 g, 4.71 mmol), [Pd2(dba)3] (129.3 mg,
0.14 mmol), CuI (26.9 mg, 0.14 mmol), and P(fur)3 (54.7 mg, 0.236 mmol) in DMSO (70 ml) in a flame-dried
Schlenk flask was degassed for 15 min, treated with dry Et3N (2.0 ml, 14.13 mmol), and stirred in the dark for
10 h. After completion, the mixture was poured onto ice/H2O, neutralized with 1n HCl and worked up normally
(Et2O, H2O). FC (AcOEt/hexane 1:10 ! 3 : 17) gave 17 (116.7 mg, 2%), 16 (4.00 g, 79%), and 18 (31.1 mg,
<1%) as white foams.

154
Helvetica Chimica Acta ± Vol. 82 (1999)
1
Table 3. Selected H-NMR (CDCl3) Chemical-Shift Values [ppm] of Monomers
H
C(1) H C(3) H C(4) H C(5) H C(6) H C(7) H C(8) H' C(8) H C(2') HO C(4) HO C(5) HO C(8)
5
7
8
±
2.48
2.57
2.56
±
±
±
±
±
3.95
3.95
3.97
3.94
3.97
4.08
3.95
3.97
3.97
3.95
4.03
4.05
4.05
4.22
4.21
3.63
3.66
3.40
3.42
3.64
3.64
3.61
3.64
3.63
3.61
3.70
3.74
3.72
3.76
3.75
3.49
3.52
3.78
3.77
3.50
3.50
3.53
3.54
3.54
3.53
3.65
3.67
3.64
3.56
3.60
2.54
2.56
2.60
2.60
2.55
2.56
2.53
2.66
2.59
2.70
2.85
2.88
2.86
2.62
2.62
3.43
3.46
3.47
3.60
3.44
3.43
3.43
3.47
3.46
3.45
3.57
3.60
3.59
3.53
3.54
3.93
3.93
3.96
4.50
3.93
3.94
3.94
3.95
3.94
3.93
4.00
3.99
4.00
3.98
4.00
3.73
3.72
3.75
4.21
3.72
3.72
3.75
3.75
3.72
3.72
3.81
3.81
3.80
3.80
3.80
±
±
±
±
±
±
±
2.24
±
±
±
±
±
±
±
±
±
2.31
2.33
2.35
±
±
±
±
±
±
±
±
±
±
2.35
2.34
±
2.08
2.00
2.03
±
9
2.57
1.99
2.36
3.03
2.51
2.44
2.49
2.53
2.53
2.55
2.40
3.18
10
11
12
13
14
15
21
±
2.01
2.40
2.21
2.05
2.12
2.13
2.11
2.09
2.05
2.40
±
±
22 2.53
23
24
25
±
±
±
Data of 5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}-
silyl}ethynyl}-6-O-(triisopropylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1! 6-C)-3,7-anhydro-1,2,6-trideoxy-
4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (16): Rf (AcOEt/hexane 1 : 4) 0.26.
M.p. 85 ± 868. [a]D25
ˆ
38.1 (c ˆ 0.7, CHCl3). IR (CHCl3): 3594w, 2962s, 2867s, 2254w, 2173w, 1602w, 1464m,
1384w, 1365w, 1328w, 1291w, 1261s, 1141m, 1098s, 1015s, 909m, 883m, 845m, 818s, 596w, 576w, 536w, 512w, 504w.
1H-NMR (500 MHz, CDCl3): 3.99 (dd, J ˆ 9.3, 0.6,
H
C(5')); 3.95 (d, J ˆ 9.3,
H C(3)); 3.94 ± 3.87
(m, H C(8), H C(10')); 3.77 (t, J ˆ 7.7, CH2CH2OSi); 3.73 ± 3.67 (m, H' C(8), H' C(10')); 3.613 (dd, J ꢁ
9.2, 8.4,
H
C(6')); 3.612 (dd, J ˆ 9.2, 8.3,
H C(4)); 3.55 ± 3.47 (m, H C(5), H C(7')); 3.45 ± 3.41
(m, H C(7), H C(9')); 2.65 (t, J ˆ 10.3, H C(6)); 2.54 (t, J ˆ 10.3, H C(8')); 2.43 (d, J ˆ 3.4, HO C(5));
2.40 (d, J ˆ 2.8, HO C(7')); 2.13 ± 2.09 (m, HO C(8), HO C(10')); 1.59 (t, J ˆ 7.7, CH2CH2OSi); 1.26 ± 1.04
(m, 3 (Me2CH)3Si); 0.95 (s, Me2C); 0.16 (s, Me3Si); 0.10 (s, Me2Si). 13C-NMR (125 MHz, CDCl3): 102.31 (s);
102.00 (s); 91.39 (s); 88.49 (s); 79.13 (d); 78.69 (d); 76.79 (d); 76.70 (d); 76.64 (s); 75.11 (d); 75.07 (d); 75.05 (s);
71.98 (d); 71.83 (d); 70.56 (s); 68.44 (s); 63.59 (t); 63.34 (t); 60.14 (t); 41.61 (t); 39.07 (d); 38.30 (d); 23.36 (2q);
18.51 (s); 18.34 ± 18.08 (several q); 13.02 (3d); 12.94 (3d); 12.00 (3d); 0.39 (3q); 4.13 (2q). MALDI-TOF-
‡
MS: 1098 ([M ‡ Na] ). Anal. calc. for C57H106O9Si5 (1075.89): C 63.63, H 9.93; found: C 63.72, H 9.73.
Data of 2,6 :11,15-Dianhydro-3,7,8,9,10,14-hexadeoxy-3,14-bis{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)-
oxy]propyl}silyl}ethynyl}-5,12-bis-O-(triisopropylsilyl)-d-erythro-l-galacto-l-gulo-hexadeca-7,9-diynitol (17): Rf
(AcOEt/hexane 1:4) 0.24. M.p. 117 ± 117.58. [a]D25
ˆ
20.6 (c ˆ 0.55, CHCl3). IR (CHCl3): 3594w, 3008m,
2961s, 2945s, 2892m, 2867s, 2400w, 2171w, 1730w, 1601w, 1524w, 1464m, 1288m, 1261s(br.), 1143m, 1096s, 1014s,
883m, 818s(br.), 602w, 577w, 539w. 1H-NMR (400 MHz, CDCl3): 4.02 (d, J ˆ 9.2, H C(6)); 3.96 ± 3.89
(m, H C(1)); 3.77 (t, J ˆ 7.7, CH2CH2OSi); 3.70 (dt, J ˆ 11.8, 6.0, H' C(1)); 3.63 (dd, J ˆ 9.1, 8.3, H C(5));
3.49 (ddd, J ˆ 10.5, 8.3, 2.8, H C(4)); 3.44 (ddd, J ˆ 10.3, 6.0, 2.7, H C(2)); 2.54 (t, J ˆ 10.3, H C(3)); 2.34
(d, J ˆ 2.7, HO C(4)); 1.98 (t, J ˆ 6.7, HO C(1)); 1.60 (t, J ˆ 7.7, CH2CH2OSi); 1.26 ± 1.05 (m, 2 (Me2CH)3Si);
0.96 (s, Me2C); 0.12 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 102.32 (s); 88.49 (s); 79.10 (d); 76.97 (s); 76.82 (d);
74.85 (d); 71.96 (d); 70.22 (s); 63.55 (t); 60.14 (t); 41.60 (t); 39.05 (d); 23.33 (2q); 18.52 (s); 18.33 ± 18.08 (several
‡
q); 12.93 (3d); 12.02 (3d); 4.13 (2q). MALDI-TOF-MS: 1327 ([M ‡ Na] ). Anal. calc. for C70H134O10Si6
(1304.34): C 64.46, H 10.35; found: C 64.58, H 10.22.
Data of 6,6'-(Buta-1,3-diyne-1,4-diyl)bis{3,7-anhydro-1,2,6-trideoxy-4-O-(triisopropylsilyl)-1-C-(trimethyl-
silyl-d-glycero-d-gulo-oct-1-ynitol} (18). Rf (AcOEt/hexane 1:2) 0.48. M.p. 251 ± 2538. [a]D25
ˆ
50.2 (c ˆ 0.85,
CHCl3). IR (CHCl3): 3596m, 3008m, 2962s, 2946s, 2867s, 2179w, 1763w, 1722m, 1602w, 1463m, 1290m, 1261s,
1252s(br.), 1142s, 1101s, 1068s, 1016s, 998s, 919w, 883s, 847s, 818s(br.), 595w, 574w, 522w. 1H-NMR (300 MHz,
CDCl3): 3.95 (d, J ˆ 9.0, H C(3)); 3.93 (dd, J ˆ 12.1, 2.5, H C(8)); 3.72 (dd, J ˆ 12.1, 5.5, H' C(8)); 3.61
(dd, J ˆ 9.0, 8.3, H C(4)); 3.53 (dd, J ˆ 10.0, 8.3, H C(5)); 3.44 (ddd, J ˆ 10.0, 5.5, 2.5, H C(7)); 2.65 (t, J ˆ
10.0, H C(6)); 2.34 (m, HO C(5), HO C(8)); 1.15 ± 1.05 (m, (Me2CH)3Si); 0.17 (s, Me3Si). 13C-NMR
(125 MHz, CDCl3): 101.98 (s); 91.44 (s); 78.71 (d); 76.17 (d); 75.18 (d); 74.56 (s); 71.94 (d); 68.71 (s); 63.42 (t);

Helvetica Chimica Acta ± Vol. 82 (1999)
155
Table 4. Selected 13C-NMR (CDCl3) Chemical-Shift Values [ppm] of Monomers
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(1')
C(2')
5
7
8
91.10
81.04
80.09
79.93
47.21
5.00
91.06
89.93
91.02
91.34
91.54
80.70
47.67
83.67
83.88
102.34
74.54
74.82
74.94
76.89
91.37
102.40
101.15
101.82
102.16
101.93
74.90
77.14
91.90
71.97
71.38
70.55
70.68
72.26
72.79
71.97
71.06
71.64
71.91
71.93
71.35
72.23
71.92
72.01
75.05
75.02
75.24
75.06
75.16
75.34
75.03
74.74
74.91
75.19
75.38
75.32
75.47
75.04
75.09
76.89
76.78
76.61
76.59
76.70
76.73
76.81
76.31
76.47
76.91
76.83
76.67
76.54
76.79
76.75
39.12
39.14
39.68
39.93
39.07
39.04
39.06
38.82
38.33
39.55
38.19
38.31
38.16
39.19
39.32
78.91
79.02
79.97
77.65
78.99
78.18
79.02
78.74
78.44
78.91
78.83
78.97
78.92
79.11
79.30
63.70
63.89
63.69
64.88
63.64
63.63
63.65
63.33
63.17
63.46
63.56
63.54
63.51
63.65
63.69
102.58
102.44
104.25
103.80
102.40
102.42
103.40
74.27
75.83
90.16
90.79
90.62
88.28
88.43
87.67
88.07
88.42
88.38
87.99
80.78
43.36
14.01
83.03
83.03
83.03
88.63
88.31
9
10
11
12
13
14
15
21
22
23
24
25
90.57
102.24
103.18
92.00
‡
38.10 (d); 18.35 (6q); 13.05 (3d); 0.40 (3q). MALDI-TOF-MS: 870 ([M ‡ Na] ). Anal. calc. for C44H78O8Si4
(847.44): C 62.36, H 9.28; found: C 62.46, H 9.30.
Coupling of 14 with 7. As described for the coupling of 10 with 13, with 14 (137.4 mg, 0.273 mmol), 7
(178.2 mg, 0.273 mmol), [Pd2(dba)3] (7.5 mg, 8.19 mmol), CuI (1.6 mg, 8.19 mmol), P(fur)3 (3.2 mg,
0.014 mmol), and dry Et3N (114 ml, 0.819 mmol) in DMSO (2.7 ml; 10 h). FC (AcOEt/hexane 1:10 ! 3 : 17)
gave 17 (10.2 mg, 3%), 16 (188.6 mg, 64%), and 18 (27.4 mg, 12%) as white foams.
Coupling of 10 with 12. As described for the coupling of 10 with 13, with 10 (1.05 g, 1.43 mmol), 12
(816.1 mg, 1.43 mmol), [Pd2(dba)3] (39.4 mg, 0.043 mmol), CuI (8.2 mg, 0.043mmol), P(fur)3 (16.7 mg,
0.072 mmol), and dry Et3N (0.6 ml, 4.30 mmol) in DMSO (14 ml; 10 h). FC (AcOEt/hexane 1:10 ! 3 : 17) gave
17 (35.5 mg, 2%). 16 (1.22g, 79%), and 18 (6.2 mg, <1%) as white foams.
Coupling of 11 with 13. As described for the coupling of 10 with 13, with 11 (971.5 mg, 1.247 mmol), 13
(530.1 mg, 1.247 mmol), [Pd2(dba)3] (34.2 mg, 0.037 mmol), CuI (7.1 mg, 0.037 mmol), P(fur)3 (14.5 mg,
0.062 mmol), and dry Et3N (0.52 ml, 3.74 mmol) in DMSO (12 ml; 10 h). FC (AcOEt/hexane 1:10 ! 3 : 17)
gave 17 (32.5 mg, 2%), 16 (1.09 g, 81%), and 18 (8.5 mg, <1%) as white foams.
Coupling of 15 with 7. As described for the coupling of 10 with 13, with 15 (175.7 mg, 0.319 mmol), 7
(208.4 mg, 0.319 mmol), [Pd2(dba)3] (8.8 mg, 9.58 mmol), CuI (1.8 mg, 9.58 mmol), P(fur)3 (1.9 mg,
0.016 mmol), and dry Et3N (67 ml, 0.479 mmol) in DMSO (3 ml; 10 h). FC (AcOEt/hexane 1:10 ! 3 : 17)
gave 17 (13.1 mg, 3%), 16 (208.9 mg, 61%), and 18 (32.8 mg, 12%) as white foams.
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-
6-O-(triisopropylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-4-O-(triiso-
propylsilyl)-d-glycero-d-gulo-oct-1-ynitol (19). Separated as byproduct upon coupling 10 and 13 in pyrrolidine
instead of Et3N (< 11%).
Data of 19: Rf (AcOEt/hexane 1 :4) 0.10. M.p. 75 ± 778. [a]D25
ˆ
50.4 (c ˆ 0.6, CHCl3). IR (CHCl3): 3597w,
3306w, 3008w, 2962s, 2867s, 2362w, 2254w, 2170w, 1602w, 1464m, 1392w, 1329w, 1261s(br.), 1097s, 1015s, 883m,
818s(br.), 602w, 577w, 509w. 1H-NMR (500 MHz, CDCl3): 4.00 (dd, J ˆ 9.3, 0.6, H C(5')); 3.97 (d, J ˆ 9.2, 2.1,
H
C(3)); 3.92 (ddd, J ꢁ 12.1, 7.1, 2.6, H C(8)); 3.90 (ddd, J ꢁ 12.1, 6.8, 2.4, H C(10')); 3.77 (t, J ˆ 7.7,
CH2CH2OSi); 3.73 ± 3.69 (m, H' C(8), H' C(10')); 3.65 (dd, J ˆ 9.3, 8.3, H C(6')); 3.64 (dd, J ˆ 9.2, 8.4,
H
H
C(4)); 3.57 ± 3.50 (m, H C(5)); H C(7')); 3.49 ± 3.42 (m, H C(9'), H C(7)); 2.68 (td, J ˆ 10.3, 0.6,
C(6)); 2.54 (t, J ˆ 10.3, H C(8')); 2.49 (d, J ˆ 2.1, H C(1)); 2.37 (d, J ˆ 3.1, HO C(5), HO C(7')); 2.00
(dd, J ˆ 7.3, 6.3, HO C(10')); 1.96 (t, J ˆ 6.8, HO C(8)); 1.59 (t, J ˆ 7.7, CH2CH2OSi); 1.26 ± 1.05
(m, 3 (Me2CH)3Si); 0.96 (s, Me2C); 0.11 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 102.27 (s); 88.59 (s); 80.76
(d); 79.11 (d); 78.79 (d); 77.23 (s); 76.73 (d); 76.71 (d); 76.43 (s); 75.13 (d); 75.04 (d); 74.75 (s); 71.86 (d); 71.42
(d); 70.48 (s); 68.57 (s); 63.64 (t); 63.36 (t); 60.15 (t); 41.64 (t); 39.11 (d); 38.33 (d); 23.27 (q); 23.34 (q); 18.53 (s);
18.34 ± 18.26 (12q); 18.08 (6q); 12.98 (3d); 12.96 (3d); 12.03 (3d); 4.12 (q); 4.14 (q). MALDI-TOF-MS:
‡
1025 ([M ‡ Na] ). Anal. calc. for C54H98O9Si4 (1003.70): C 64.62, H 9.84; found: C 64.45, H 9.76.

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Helvetica Chimica Acta ± Vol. 82 (1999)
3,7-Anhydro-1,2,6-trideoxy-6-C-[(4-nitrophenyl)ethynyl]-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glycero-
d-gulo-oct-1-ynitol (21). At 508, a soln. of [Pd(PPh3)4] (30.1 mg, 0.026 mmol), CuI (15.6 mg, 0.082 mmol), and
1-iodo-4-nitrobenzene (900 mg, 3.62 mmol) in dry, degassed DMSO (24 ml) was treated dropwise with a soln. of
13 (512 mg, 1.21 mmol) in dry Et3N (9 ml) and stirred overnight. Dilution with AcOEt (25 ml), neutralization
with 2n aq. HCl (pH 7), normal workup (AcOEt, H2O), and FC (AcOEt/hexane 1:4) gave 21 (0.650 g, 98%).
Yellow powder. Rf (AcOEt/hexane 1:2) 0.49. M.p. 146 ± 1478. [a]D25
3598w, 2963m, 2946m, 2867m, 2226w, 2180w, 1726w, 1595m, 1522s, 1464w, 1346s, 1144m, 1108m, 1066m, 995w,
884m, 855s. 1H-NMR (300 MHz, CDCl3): 8.16 (d, J ˆ 9.0), 7.56 (d, J ˆ 9.0, 4 arom. H); 4.03 (d, J ˆ 9.3,
ˆ
41.7 (c ˆ 0.50, CHCl3). IR (CCl4):
H
H
C(3)); 4.00 (ddd, J ꢁ 12.0, 7.4, 2.6, H C(8)); 3.81 (dt, J ꢁ 11.9, 5.9, H' C(8)); 3.70 (dd, J ˆ 9.0, 8.2,
C(4)); 3.65 (td, J ˆ 8.2, 3.0, H C(5)); 3.57 (ddd, J ˆ 10.3, 5.6, 2.5, H C(7)); 2.85 (t, J ˆ 10.2, H C(6)); 2.53
(d, J ˆ 3.0, HO C(5)); 2.13 (dd, J ˆ 7.2, 6.4, HO C(8)); 1.31 ± 1.12 (m, (Me2CH)3Si); 0.19 (s, Me3Si). 13C-NMR
(75 MHz, CDCl3): 147.14 (s); 132.60 (2d), 129.42 (s); 123.55 (2d); 101.93 (s); 91.54 (s); 90.79 (s); 83.03 (s); 78.83
(d); 76.83 (d); 75.38 (d); 71.93 (d); 63.56 (t); 38.19 (d); 18.32 (6q); 13.08 (3d); 0.42 (3q). CI-MS: 563 (100,
‡
‡
‡
[M ‡ NH4] ), 546 (22, [M ‡ 1] ), 516(69), 472(51), 442(74), 309(54), 148(37), 131(41), 73 (37, Me3Si ).
Anal. calc. for C28H43NO6Si2 (545.82): C 61.61, H 7.94, N 2.57; found: C 61.44, H 7.99, N 2.53.
3,7-Anhydro-1,2,6-trideoxy-6-C-[(4-nitrophenyl)ethynyl]-4-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-
ynitol (22). At 228, a soln. of 21 (299.7 mg, 0.5491 mmol) in MeOH (20 ml) was treated dropwise with a soln. of
0.25m MeONa in MeOH (0.5 ml) and stirred for 23 h. Addition of Amberlite IR-20, filtration, evaporation, and
FC (AcOEt/hexane 1:3) gave 22 (204.6 mg, 79%). Yellow syrup. Rf (AcOEt/hexane 1:4) 0.12. [a]D25
ˆ
37.4
(c ˆ 0.43, CHCl3). IR (CCl4): 3606m, 3311m, 2945m, 2868m, 2225w, 1740w, 1596m, 1558w, 1525s, 1464w, 1344s,
1286w, 1244w, 1143m, 1124m, 1100m, 1069m, 962w, 883m, 856m, 669m, 641m. 1H-NMR (300 MHz, CDCl3): 8.18
(d, J ˆ 8.9), 7.56 (d, J ˆ 8.9, 4 arom. H); 4.05 (dd, J ˆ 9.0, 2.1, H C(3)); 4.00 ± 3.97 (m, H C(8)); 3.83 ± 3.80
(m, H' C(8)); 3.74 (dd, J ˆ 9.0, 8.3, H C(4)); 3.67 (td, J ˆ 8.3, 3.1, H C(5)); 3.60 (ddd, J ˆ 10.4, 5.5, 2.5,
H
C(7)); 2.88 (t, J ˆ 10.3, H C(6)); 2.53 (d, J ˆ 2.1, H C(1), HO C(5)); 2.11 (br. s, HO C(8)); 1.30 ± 1.12
(m, (Me2CH)3Si). 13C-NMR (75 MHz, CDCl3): 147.16 (s); 132.60 (2d); 129.35 (s); 123.55 (2d); 90.62 (s); 83.03
(s); 80.70 (d); 78.97 (d); 76.67 (d); 75.32 (d); 74.90 (s); 71.35 (d); 63.54 (t); 38.21 (d); 18.33 (6q); 13.02 (3d). CI-
‡
‡
MS: 491 (100, [M ‡ NH4] ), 474 (13, [M ‡ 1] ), 444(17), 282(11), 237(29), 148(11). Anal. calc. for
C25H35NO6Si (473.64): C 63.40, H 7.45, N 2.96; found: C 63.22, H 7.29, N 2.88.
3,7-Anhydro-1-C-bromo-1,2,6-trideoxy-6-C-[(4-nitrophenyl)ethynyl]-4-O-(triisopropylsilyl)-d-glycero-d-
gulo-oct-1-ynitol (23). A soln. of 21 (33 mg, 0.0604 mmol) and NBS (36.3 mg, 0.2039 mmol) in dry acetone
(1.5 ml) was treated with AgOCOCF3 (1.2 mg, 5.4 mmol) and stirred in the dark (Al foil) at 218 for 43 h. After
completion, the mixture was normally worked up (Et2O, H2O). HPLC (Si 60; AcOEt/hexane 2 :8, 10 ml/min;
RID detection) gave 23 (25.3 mg, 76%). Yellow foam.
At 218, a soln. of 22 (0.0275 g, 0.0468 mmol) and NBS (9.2 mg, 0.0514 mmol) in dry acetone (1.5 ml) was
treated with AgOCOCF3 (0.3 mg, 1.4 mmol) and stirred in the dark (Al foil) at 218 for 3 h. After completion, the
mixture was worked up normally (Et2O, H2O). FC (AcOEt/hexane 1:4) gave 23 (30.4 mg, 97%). Yellow foam.
Rf (AcOEt/hexane 1:2) 0.37. M.p. 70 ± 728. [a]D25
ˆ
43.4 (c ˆ 0.23, CHCl3). IR (CCl4): 3606m, 2946m, 2868m,
2223w, 1734w, 1596m, 1525s, 1494w, 1464w, 1345s, 1287w, 1244w, 1142s, 1120s, 1068m, 1015w, 1000w, 920w, 883m,
856s, 686m. 1H-NMR (300 MHz, CDCl3): 8.18 (d, J ˆ 8.9), 7.56 (d, J ˆ 8.9, 4 arom. H); 4.05 (d, J ˆ 8.9,
H
H
H
C(3)); 4.00 (ddd, J ˆ 11.8, 6.9, 2.0, H C(8)); 3.80 (dt, J ꢁ 12.0, 6.0, H' C(8)); 3.72 (dd, J ˆ 8.9, 8.3,
C(4)); 3.64 (ddd, J ˆ 10.3, 8.3, 3.1, H C(5)); 3.59 (ddd, J ˆ 10.4, 5.5, 2.4, H C(7)); 2.86 (t, J ˆ 10.1,
C(6)); 2.55 (br. s, HO C(5)); 2.09 (br. s, HO C(8)); 1.30 ± 1.11 (m, (Me2CH)3Si). 13C-NMR (75 MHz,
CDCl3): 147.17 (s); 132.60 (2d); 129.33 (s); 123.55 (2d); 90.57 (s); 83.03 (s); 78.92 (d); 77.14 (s); 76.58 (d); 75.47
‡
(d); 72.23 (d); 63.51 (t); 47.67 (s); 38.16 (d); 18.21 (6q); 12.94 (3d). CI-MS: 570 (30, [M ‡ NH4] ), 569(89),
‡
568(14), 552 (12, M ), 550(5), 450(13), 448(12), 317(17), 315(17), 225(11), 160(10), 150(11), 148(40),
131(19), 130(12), 120(15), 103(12), 35(31). Anal. calc. for C25H34BrNO6Si (552.54): C 54.34, H 6.20, N 2.53;
found: C 54.22, H 6.42, N 2.72.
3,7-Anhydro-1,2,6-trideoxy-6-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-1-
C-(4-nitrophenyl)-4-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (24). Similarly as described for 21, with 7
(95.5 mg, 0.146 mmol), 1-iodo-4-nitrobenzene (36.35 mg, 0.438 mmol), Et3N (0.5 ml), [Pd(PPh3)4] (3.64 mg,
3.15 mmol), CuI (1.89 mg, 9.9 mmol), and DMSO (4 ml). FC (AcOEt/hexane 1:9) gave 24 (99.8 mg, 88%).
Transparent syrup. Rf (AcOEt/hexane 1:4) 0.32. [a]D25
ˆ
23.1 (c ˆ 0.315, CHCl3). IR (CCl4): 3607m, 2944s,
2867s, 2170w, 1596m, 1525s, 1494w, 1464m, 1384w, 1345s, 1291w, 1253m, 1142s, 1092s, 1014m, 997m, 919w, 883s,
855s, 840m, 685s. 1H-NMR (500 MHz, CDCl3): 8.20 (d, J ˆ 9.0), 7.57 (d, J ˆ 9.0, 4 arom. H); 4.22 (d, J ˆ 9.3,
H
H
C(3)); 3.98 (ddd, J ˆ 12.0, 7.2, 2.6, H C(8)); 3.80 ± 3.76 (m, H' C(8), CH2CH2OSi); 3.76 (dd, J ˆ 9.3, 8.3,
C(4)); 3.56 (ddd, J ˆ 10.3, 8.3, 2.8, H C(5)); 3.53 (ddd, J ˆ 10.3, 5.9, 2.6, H C(7)); 2.62 (t, J ˆ 10.3,

Helvetica Chimica Acta ± Vol. 82 (1999)
157
H
C(6)); 2.40 (d, J ˆ 2.7, HO C(5)); 2.05 (t, J ꢁ 6.6, H C(8)); 1.61 (t, J ˆ 7.7, CH2CH2OSi); 1.21 ± 1.06
(m, (Me2CH)3Si); 0.98 (s, Me2C); 0.13 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 147.38 (s); 132.46 (2d); 129.10
(s); 123.61 (2d); 102.24 (s); 91.90 (s); 88.63 (s); 83.87 (s); 79.11 (d); 76.79 (d); 75.04 (d); 71.92 (d); 63.65 (t);
60.11 (t); 41.61 (t); 39.19 (d); 23.32 (2q); 18.50 (s); 18.24 (6q); 18.06 (6q); 12.94 (3d); 11.98 (3d); 4.14 (2q).
‡
CI-MS: 774 (12, M ), 665(9), 431(10), 429(7), 156(13), 145(23). Anal. calc. for C41H71NO7Si3 (774.27):
C 63.60, H 9.24, N 1.81; found: C 63.49, H 9.14, N 1.95.
3,7-Anhydro-1,2,6-trideoxy-6-C-{[(3-hydroxy-1,1-dimethylpropyl)dimethylsilyl]ethynyl}-1-C-(4-nitrophenyl)-
4-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (25). At 508, a soln. of 24 (399.8 mg, 0.516 mmol) in EtOH
(10 ml) was treated with 0.1n HCl (2 ml) and stirred for 3 h. After completion, the solvent was removed under
reduced pressure. FC (AcOEt/hexane 1 :4) gave 25 (287.3 mg, 90%). White solid. Rf (AcOEt/hexane 1:2) 0.20.
[a]2D5
ˆ
35.5 (c ˆ 0.36, CHCl3). IR (CHCl3): 3597m, 2963s, 2867s, 2359w, 2171w, 1596m, 1558w, 1540w, 1522m,
1494w, 1464m, 1411m, 1346s, 1262s, 1096s, 1014s, 882m, 856s, 818s, 603w. 1H-NMR (300 MHz, CDCl3): 8.19
(d, J ˆ 9.0), 7.57 (d, J ˆ 9.0, 4 arom. H); 4.23 (d, J ˆ 9.2, H C(3)); 4.01 ± 3.95 (m, H C(8)); 3.82 ± 3.72
(m, H' C(8)); 3.80 (br. t, J ˆ 7.2, CH2OH); 3.75 (dd, J ˆ 9.2, 8.3, H C(4)); 3.63 ± 3.55 (m, H C(5)); 3.54
(ddd, J ˆ 10.2, 5.7, 2.4,
H
C(7)); 3.18 (d, J ˆ 3.2, HO C(5)); 2.62 (t, J ˆ 10.3,
H C(6)); 2.41 ± 2.38
(m, HO C(8)); 1.86 ± 1.82 (m, CH2CH2OH); 1.62 (t, J ˆ 7.2, CH2CH2OH); 1.19 ± 1.07 (m, (Me2CH)3Si); 0.97
(s, Me2C); 0.13 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 147.40 (s); 132.49 (2d); 129.14 (s); 123.64 (2d); 103.18
(s); 92.00 (s); 88.31 (s); 83.88 (s); 79.30 (d); 76.75 (d); 75.09 (d); 72.01 (d); 63.69 (t); 60.11 (t); 43.03 (t); 39.32
‡
‡
(d); 24.16 (2q); 18.52 (s); 18.29 (6q); 12.96 (3d); 3.95 (2q). CI-MS: 618 (1, [M‡ 1] ), 474 (5, [M DOPS‡ 1] ),
‡
444(9), 370(10), 306(3), 162(10), 146 (22, DOPS ), 145(100), 129(21), 75(21), 74(12). Anal. calc. for
C32H51NO7Si2 (617.89): C 62.20, H 8.32, N 2.27; found: C 62.05, H 8.47, N 2.06.
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-[(4-nitrophenyl)ethynyl]-6-O-(triisopropylsilyl)-d-glycero-d-gulo-
deca-1,3-diynitol-1-yl-(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-d-glyc-
ero-d-gulo-oct-1-ynitol (26). At 228, a soln. of 23 (83.4 mg, 0.151 mmol), 13 (64.13 mg, 0.151 mmol),
[Pd2(dba)3] (4.12 mg, 0.0045 mmol), CuI (0.74 mg, 0.0039 mmol), and LiI (4.0 mg, 0.030 mmol) in DMSO
(3.6 ml) in a flame-dried Schlenk flask was degassed for 15 min, treated with dry PMP (0.076 ml, 0.422 mmol),
and stirred in the dark for 10 h. After completion, the mixture was poured onto ice/H2O, neutralized with 1n HCl
and worked up normally (Et2O, H2O). FC (AcOEt/hexane 1 : 3) gave 26 (183.3 mg, 94%). White powder. Rf
(AcOEt/hexane 1 : 2) 0.19. M.p. 1388. [a]D25
ˆ
63.5 (c ˆ 0.17, CHCl3). IR (CCl4): 3604m, 3497w(br.), 2946s,
2867s, 2256w, 2226w, 2185w, 1596m, 1525s, 1464m, 1345s, 1289m, 1252m, 1143s, 1120s, 1069m, 997m, 883m, 855s,
684m. 1H-NMR (500 MHz, CDCl3): 8.17 (d, J ˆ 9.0), 7.55 (d, J ˆ 9.0, 4 arom. H); 4.07 (dd, J ˆ 9.0, 0.8,
H
H
C(5')); 3.98 (ddd, J ꢁ 12.2, 6.9, 2.4, H C(10')); 3.96 (d, J ˆ 9.3, H C(3)); 3.91 (ddd, J ˆ 12.0, 7.2, 2.5,
C(8)); 3.79 (dt, J ꢁ 12.0, 6.0, H' C(10')); 3.71 (dd, J ꢁ 9.8, 8.9, H C(4)); 3.70 (dt, J ꢁ 12.1, 5.9, H' C(8));
3.66 (ddd, J ˆ 10.2, 8.4, 3.2, H C(7')); 3.63 (dd, J ˆ 9.2, 8.3, H C(6')); 3.57 (ddd, J ˆ 10.3, 5.4, 2.4, H C(9'));
3.53 (ddd, J ˆ 10.4, 8.3, 3.3, H C(5)); 3.44 (ddd, J ˆ 10.3, 5.7, 2.5, H C(7)); 2.86 (t, J ˆ 10.2, H C(8')); 2.67
(t, J ˆ 10.3, H C(6)); 2.50 (d, J ˆ 3.1, HO C(7')); 2.37 (d, J ˆ 3.3, HO C(5)); 2.01 (t, J ꢁ 6.7, HO C(8),
HO C(10')); 1.27 ± 1.10 (m, 2 (Me2CH)3Si); 0.17 (s, Me3Si). 13C-NMR (125 MHz, CDCl3): 147.27 (s); 132.64
(2d); 129.33 (s); 123.59 (2d); 101.94 (s); 91.49 (s); 90.48 (s); 83.14 (s); 79.06 (d); 78.67 (d); 76.93 (s); 76.85 (d);
76.68 (d); 75.47 (d); 75.13 (d); 74.63 (s); 72.01 (d); 71.86 (d); 70.88 (s); 68.33 (s); 63.53 (t); 63.36 (t); 38.25 (d);
38.23 (d); 18.34 (6q); 18.28 ± 18.25 (6q); 13.04 (3d); 12.99 (3d); 0.40 (3q). MALDI-TOF-MS: 919 ([M ‡
‡
Na] ). Anal. calc. for C47H73NO10Si3 (896.35): C 62.98, H 8.21, N 1.56; found: C 62.74, H 7.96, N 1.40.
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-[(4-nitrophenyl)ethynyl]-6-O-(triisopropylsilyl)-d-glycero-d-gulo-
deca-1,3-diynitol-1-yl-(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-1-C-(4-nitrophenyl)-4-O-(triisopropylsilyl)-d-glyc-
ero-d-gulo-oct-1-ynitol (27). At 228, a soln. of 25 (97.4 mg, 0.1576 mmol), 23 (87.1 mg, 0.1576 mmol),
[Pd2(dba)3] (4.3 mg, 4.73 mmol), CuI (0.9 mg, 4.73 mmol), and LiI (4.2 mg, 0.032 mmol) in DMSO (2 ml) in a
flame-dried Schlenk flask was degassed for 15 min, treated with dry PMP (86 ml, 0.473 mmol), and stirred in the
dark for 14 h. After completion, the mixture was poured onto ice/H2O, neutralized with 1n HCl and worked up
normally (Et2O, H2O). FC (AcOEt/hexane 1 : 3) gave 27 (68.5 mg, 46%). White solid. Rf (AcOEt/hexane 1 : 2)
0.21. M.p. 229 ± 2358. [a]D25
ˆ
48.4 (c ˆ 0.31, CHCl3). IR (CHCl3): 3603m, 3444w(br.), 3008m, 2963s, 2868s,
2230w, 2226w, 1732w, 1596m, 1522s, 1493w, 1464m, 1346s, 1262s, 1094s, 1015s, 882m, 856m, 818s, 639w, 576w.
1H-NMR (500 MHz, CDCl3): 8.20 (d, J ˆ 9.0), 8.18 (d, J ˆ 9.0), 7.57 (d, J ˆ 9.0), 7.56 (d, J ˆ 9.0, 8 arom. H);
4.23 (d, J ˆ 9.3, H C(3)); 4.08 (dd, J ˆ 9.1, 0.7, H C(5')); 3.99 (ddd, J ˆ 12.1, 7.0, 2.4, H C(10')); 3.95
(ddd, J ˆ 12.1, 6.8, 2.4, H C(8)); 3.82 ± 3.77 (m), 3.78 ± 3.73 (m, H' C(8), H' C(10')); 3.76 (dd, J ˆ 9.3, 8.3,
H
H
H
C(4)); 3.72 (dd, J ˆ 9.1, 8.4, H C(6')); 3.66 (dd, J ˆ 10.2, 8.3, 3.1, H C(7')); 3.62 (ddd, J ˆ 10.3, 8.3, 3.3,
C(5)); 3.58 (ddd, J ˆ 10.4, 5.4, 2.4, H C(9')); 3.54 (ddd, J ˆ 10.3, 5.4, 2.4, H C(7)); 2.86 (t, J ˆ 10.2,
C(8')); 2.75 (td, J ꢁ 10.3, 0.5, H C(6)); 2.51 (d, J ˆ 3.2, HO C(7')); 2.41 (d, J ˆ 3.3, HO C(5)); 2.01

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Helvetica Chimica Acta ± Vol. 82 (1999)
(t, J ˆ 6.9, HO C(10')); 1.96 (t, J ˆ 6.6, HO C(8)); 1.19 ± 1.09 (m, 2 (Me2CH)3Si). 13C-NMR (75 MHz,
CDCl3): 147.92 (s); 147.67 (s); 133.11 (2d); 132.96 (2d); 129.77 (s); 129.38 (s); 124.11 (2d); 124.03 (2d); 91.88
(s); 90.88 (s); 84.49 (s); 83.47 (s); 79.52 (d); 79.28 (d); 76.95 (2d); 75.74 (d); 75.45 (d); 75.24 (s); 72.29 (d); 72.16
(d); 71.13 (s); 68.81 (s); 63.72 (t); 63.61 (t); 38.68 (d); 38.48 (d); 18.50 (12q); 13.18 (3d); 13.11 (3d); 1s missing.
‡
‡
FAB-MS: 946 (63, [M ‡ 1] ), 945 (100, M ), 901(91), 841(62), 696(70), 652(58), 613(63). Anal. calc. for
C50H68N2O12Si2 (945.26): C 63.53, H 7.25, N 2.96; found: C 63.48, H 7.18, N 2.86.
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-{{dimethyl{1,1-dimethyl-3-[(triisopropylsilyl)oxy]propyl}silyl}ethynyl}-
6-O-(triisopropylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-1-C-(4-
nitrophenyl)-4-O-(triisopropylsilyl)-d-glycero-d-gulo-oct-1-ynitol (28). At 228,
a soln. of 25 (99.9 mg,
0.1617 mmol), 10 (118.4 mg, 0.1617 mmol), [Pd2(dba)3] (4.4 mg, 4.85 mmol), CuI (0.9 mg, 4.85 mmol), and
LiI (4.3 mg, 0.323 mmol) in DMSO (2 ml) in a flame-dried Schlenk flask was degassed for 15 min, treated with
dry PMP (88 ml, 0.485 mmol), and stirred in the dark for 14 h. After completion, the mixture was poured onto
ice/H2O, neutralized with 1n HCl and worked up normally (Et2O, H2O). FC (AcOEt/hexane 1 : 3) gave 28
(72.7 mg, 40%). White powder. Rf (AcOEt/hexane 1 : 3) 0.20. M.p. 87 ± 88.58. [a]D25
ˆ
31.4 (c ˆ 0.41, CHCl3).
IR (CHCl3): 3599w, 2963s, 2867m, 2359w, 2168w, 1596w, 1522m, 1464m, 1412m, 1346m, 1262s, 1095s, 1015s,
856m, 818s, 600w, 508w. 1H-NMR (500 MHz, CDCl3): 8.20 (d, J ˆ 9.0), 7.57 (d, J ˆ 9.0, 4 arom. H); 4.23 (d, J ˆ
9.3, H C(3)); 4.00 (dd, J ˆ 9.2, 0.7, H C(5')); 3.94 (ddd, J ˆ 12.1, 7.0, 2.5, H C(8)); 3.92 (ddd, J ˆ 12.2, 7.4,
2.5, H C(10')); 3.77 (t, J ˆ 7.7, CH2CH2OSi); 3.75 (dd, J ˆ 9.3, 8.4, H C(4)); 3.78 ± 3.72 (m), 3.74 ± 3.69
(m, H' C(8), H' C(10')); 3.65 (dd, J ˆ 9.2, 8.4, H C(6')); 3.61 (ddd, J ˆ 10.3, 8.3, 3.3, H C(5)); 3.53
(ddd, J ˆ 10.3, 5.4, 2.4, H C(7)); 3.51 (ddd, J ˆ 10.6, 8.4, 2.8, H C(7')); 3.45 (ddd, J ˆ 10.3, 6.0, 2.5, H C(9'));
2.73 (td, J ꢁ 10.2, 0.5, H C(6)); 2.55 (t, J ˆ 10.3, H C(8')); 2.39 (d, J ˆ 3.3, HO C(5)); 2.37 (d, J ˆ 2.8,
HO C(7')); 1.97 (dd, J ˆ 7.3, 6.2, HO C(8)); 1.93 (t, J ˆ 6.7, HO C(10')); 1.60 (t, J ˆ 7.7, CH2CH2OSi);
1.23 ± 1.08 (m, 3 (Me2CH)3Si); 0.96 (s, Me2C); 0.11 (s, Me2Si). 13C-NMR (75 MHz, CDCl3): 147.74 (s); 132.76
(2d); 129.23 (s); 123.91 (2d); 102.46 (s); 91.75 (s); 88.69 (s); 84.24 (s); 79.34 (d); 79.08 (d); 76.82 (2d); 76.47 (s);
75.41 (s); 75.21 (2d); 72.09 (d); 71.96 (d); 70.58 (s); 68.81 (s); 63.69 (t); 63.42 (t); 60.25 (t); 41.67 (t); 39.13 (d);
38.50 (d); 23.32 (2q); 18.54 (s); 18.30 ± 18.10 (18q); 12.96 (3d); 12.93 (3d); 12.03 (3d); 4.16 (2q). MALDI-
‡
TOF-MS: 1148 ([M ‡ Na] ). Anal. calc. for C60H101NO11Si4 (1124.74): C 64.07, H 9.05, N 1.25; found: C 64.15,
H 9.02, N 1.25.
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-{[(3-hydroxy-1,1-dimethylpropyl)dimethylsilyl]ethynyl}-6-O-(tri-
isopropylsilyl)-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-4-O-(triisopropyl-
silyl)-1-C-(trimethylsilyl)-d-glycero-d-gulo-oct-1-ynitol (29). A soln. of 16 (870.1 mg, 0.81 mmol) in EtOH
(15 ml) was treated with 0.1n HCl (4.6 ml) and stirred at 508 for 3 h. The solvent was removed under reduced
pressure. FC (AcOEt/hexane 1 : 2 ! 1 : 1) gave 29 (677.8 mg, 91%). White foam. Rf (AcOEt/hexane 4 : 6) 0.27.
M.p. 112 ± 1148. [a]D25
ˆ
44.4 (c ˆ 0.6, CHCl3). IR (CHCl3): 3598m, 3424w(br.), 3007m, 2962s, 2946s, 2892s,
2867s, 2261w, 2173m, 1602w, 1464m, 1385w, 1366m, 1329m, 1291m, 1261s(sh), 1143s, 1100s, 1016s, 883s, 845s,
818s, 600w, 575w. 1H-NMR (500 MHz, CDCl3): 4.01 (dd, J ˆ 9.3, 0.7, H C(5')); 3.96 (d, J ˆ 9.3, H C(3));
3.92 ± 3.87 (m, H C(8), H C(10')); 3.78 (td, J ˆ 7.0, 6.1, CH2OH); 3.73 ± 3.67 (m, H' C(8), H' C(10')); 3.63
(dd, J ˆ 9.2, 8.1, H C(6')); 3.62 (dd, J ˆ 9.2, 8.0, H C(4)); 3.54 ± 3.50 (m, H C(5), H C(7')); 3.45 (ddd, J ˆ
10.6, 5.8, 2.5, H C(9')); 3.43 (ddd, J ˆ 10.4, 5.7, 2.5, H C(7)); 3.05 (d, J ˆ 3.3, HO C(7')); 2.65 (t, J ˆ 10.3,
H
C(6)); 2.55 (t, J ˆ 10.3, H C(8')); 2.39 (d, J ˆ 3.3, HO C(5)); 2.15 ± 2.13 (m, HO C(8)); 2.06 (t, J ˆ 6.7,
HO C(10')); 2.04 (d, J ˆ 6.2, CH2OH); 1.61 (t, J ˆ 7.0, CH2CH2OH); 1.26 ± 1.04 (m, 2 (Me2CH)3Si); 0.96
(s, Me2C); 0.17 (s, Me3Si); 0.12 (s, Me2Si). 13C-NMR (125 MHz, CDCl3): 103.13 (s); 102.01 (s); 91.40 (s); 88.25
(s); 79.22 (d); 78.68 (d); 76.83 (d); 76.69 (d); 76.60 (s); 75.13 (d); 75.08 (d); 72.01 (d); 71.91 (d); 70.52 (s); 68.47
(s); 63.68 (t); 63.36 (t); 60.11 (t); 43.04 (t); 39.18 (d); 38.31 (d); 24.13 (2q); 19.07 (s); 18.35 ± 18.27 (several q);
‡
13.03 (3d); 12.95 (3d); 0.39 (3q); 3.97 (q); 4.00 (q); 1s missing. MALDI-TOF-MS: 942 ([M ‡ Na] ).
Anal. calc. for C48H86O9Si4 (919.55): C 62.70, H 9.43; found: C 62.52, H 9.19.
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-[(4-nitrophenyl)ethynyl]-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-
(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-d-glycero-d-gulo-oct-1-ynitol (30). At 228,
a soln. of 26 (17.7 mg,
0.01975 mmol) in dry MeOH (2 ml) was treated with freshly prepared 0.25m MeONa in MeOH (0.2 ml) and
stirred for 8 h. After the addition of Amberlite IR-120, the mixture was filtered, and the filtrate was evaporated
under reduced pressure to give 31. Strirring of 31 in 0.3n HCl/MeOH at 558 during 36 h gave 30 (8.9 mg, 92%)
as a beige powder.
At 08, a soln. of 26 (21.3 mg, 0.0238 mmol) in THF (1.5 ml) was treated dropwise with a soln. of Bu4NF ´
3 H2O (21.0 mg, 0.0665 mmol) in THF (1.5 ml) and stirred for 6 h. Normal workup (AcOEt, H2O) and FC
(AcOEt/hexane 9 : 1) gave 30 (3.4 mg, 29%). White powder. Rf (AcOEt/hexane 9 : 1) 0.09. M.p. 2158 (dec.). IR
(KBr): 3569m (br.), 3422m(br.), 2922w, 2259w, 2127w, 1629w, 1570w, 1534w, 1508w, 1458w, 1375w, 1250w,

Helvetica Chimica Acta ± Vol. 82 (1999)
159
Table 5. Selected 13C-NMR (CDCl3) Chemical-Shift Values [ppm] of Dimers
16
19
26
27
28
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(1')
C(2')
C(3')
C(4')
C(5')
C(6')
C(7')
C(8')
C(9')
C(10')
C(1'')
C(2'')
91.39
102.00
71.98
75.07
76.79
38.50
78.69
63.34
76.64
68.44
70.56
75.05
71.83
75.11
76.70
39.07
79.13
63.59
102.31
88.49
80.76
77.23
71.42
75.04
76.73
38.33
78.79
63.36
76.43
68.57
70.48
74.75
71.86
75.13
76.71
39.11
79.11
63.64
102.27
88.59
91.49
101.94
71.86
75.13
76.85
38.23
78.67
63.36
74.63
68.33
70.88
76.93
72.01
75.47
76.68
38.25
79.06
63.53
90.48
83.14
84.49
91.88
72.16
75.74
76.95
38.48
79.28
63.61
75.24
68.81
71.13
84.24
91.75
71.96
75.21
76.82
38.50
79.34
63.42
75.41
68.81
70.58
76.47
72.09
75.21
76.82
39.13
79.08
63.69
102.46
88.69
a
)
72.29
75.45
76.95
38.68
79.52
63.72
90.88
83.47
a) Hidden by other signals.
1
1182w, 1075m, 1051m, 990w, 961w, 883w, 641w, 579w, 529w, 437w. H-NMR (300 MHz, CD3OD): 8.20 (d, J ˆ
8.7), 7.64 (d, J ˆ 8.7, 4 arom. H)); 4.07 (d, J ˆ 9.7, H C(5')); 3.93 (dd, J ˆ 9.6, 2.2, H C(3)); 3.94 ± 3.64
(m, 2 H C(8), 2 H C(10')); 3.54 ± 3.41 (m, H C(5),
H
C(7),
H
C(7'),
H C(9')); 3.31 ± 3.25
(m, H C(4)); 3.21 (dd, J ˆ 9.5, 8.4, H C(6')); 2.88 (d, J ˆ 2.2, H C(1)); 2.78 (t, J ˆ 10.3, H C(8')); 2.61
(t, J ˆ 10.3, H C(6)). 13C-NMR (75 MHz, CD3OD): 147.27 (s); 132.74 (2d); 129.31 (s); 123.59 (2d); 90.52 (s);
83.17 (s); 81.81 (d); 81.41 (d); 80.95 (d); 78.68 (d); 78.00 (d); 77.32 (s); 76.56 (s); 75.57 (s, d); 75.44 (d); 72.64
(2d); 71.13 (s); 68.81 (s); 63.69 (t); 63.42 (t); 38.25 (d); 38.23 (d).
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-[(4-nitrophenyl)ethynyl]-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-
(1 ! 6-C)-3,7-anhydro-1,2,6-trideoxy-1-C-(4-nitrophenyl)-d-glycero-d-gulo-oct-1-ynitol (32). At 558, a soln. of
27 (26.2 mg, 0.0277 mmol) in 0.3n HCl/MeOH (2.5 ml) was stirred for 45 h. Evaporation and FC (AcOEt/
hexane 9 : 1) gave 32 (16.8 mg, 97%). Beige powder. Rf (AcOEt/hexane 9 : 1) 0.08. M.p. 2228 (dec.). IR (KBr):
3573m(br.), 3423m(br.), 2923w, 2261w, 2127w, 1629w, 1570w, 1560w, 1534w, 1508w, 1376w, 1251w, 1182m,
1075m, 1051m, 990w, 961w, 883m, 640w, 531w. 1H-NMR (300 MHz, CD3OD): 8.20 (d, J ˆ 8.4), 7.65 (d, J ˆ 8.6,
4 arom. H); 8.17 (d, J ˆ 8.3), 7.62 (d, J ˆ 8.4, 4 arom. H); 4.21 (d, J ˆ 9.0, H C(3)); 4.06 (dd, J ˆ 9.0, 0.7,
H
H
C(5')); 3.92 ± 3.84 (m, H C(8), H C(10')); 3.76 ± 3.62 (m, H' C(8), H' C(10')); 3.53 ± 3.47 (m, H C(5),
C(7), H C(7'), H C(9')); 3.33 ± 3.20 (m, H C(4), H C(6')); 2.77 ± 2.54 (m, H C(6), H C(8')).
13C-NMR (75 MHz, CD3OD): 147.93 (s); 147.67 (s); 133.12 (2d); 132.98 (2d); 129.77 (s); 129.34 (s); 124.12
(2d); 124.01 (2d); 91.89 (s); 90.91 (s); 84.49 (s); 83.47 (s); 81.39 (d); 80.93 (d); 78.67 (d); 78.00 (d); 76.43 (s);
75.57 (d); 75.44 (d); 75.05 (s); 72.63 (d); 72.61 (d); 71.13 (s); 68.82 (s); 63.74 (2t); 38.69 (d); 38.48 (d).
5,9-Anhydro-1,2,3,4,8-pentadeoxy-8-C-ethynyl-d-glycero-d-gulo-deca-1,3-diynitol-1-yl-(1 ! 6-C)-3,7-an-
hydro-1,2,6-trideoxy-1-C-(4-nitrophenyl)-d-glycero-d-gulo-oct-1-ynitol (35). At 508, a soln. of 28 (13.0 mg,
0.0116 mmol) in EtOH (2 ml) was treated with 0.1n HCl (0.9 ml) and stirred for 12 h. After completion, the
solvent was removed under reduced pressure and gave 33 (12.1 mg). At 228, a soln. of 33 (12.1 mg raw) in
MeOH (2 ml) was treated with Et3N (0.1 ml) and stirred for 10 h. Evaporation and FC (AcOEt/hexane 4 : 7)
gave 34 (7.2 mg). Refluxing a soln. of 34 (7.2 mg, 9.02 mmol) in 0.3n HCl/MeOH (5 ml) during 52 h,
evaporation, washing with hexane and ice-cold H2O gave 35 (4.3 mg, 75%). Beige powder. Rf (AcOEt/hexane
9 : 1) 0.07. M.p. 2228 (dec.). IR (KBr): 3571m(br.), 3423m, 2923w, 2259w, 2127w, 1629w, 1570w, 1560w, 1534w,
1508w, 1376w, 1250w, 1182m, 1075m, 1051m, 990w, 961w, 883w, 641w, 579w, 529w. 1H-NMR (300 MHz,
CD3OD): 8.17 (d, J ˆ 8.3), 7.62 (d, J ˆ 8.4, 4 arom. H); 4.23 (d, J ˆ 9.7, H C(3)); 4.02 (d, J ˆ 9.7, H C(5));

160
Helvetica Chimica Acta ± Vol. 82 (1999)
3.89 ± 3.64 (m, 2 H C(8), 2 H C(10')); 3.53 ± 3.43 (m, H C(5), H C(7), H C(7'), H C(9')); 3.31 ± 3.22
(m, H C(4), H C(6')); 2.59 (t, J ꢁ 10.3, H C(6)); 2.54 (d, J ˆ 2.2, H C(2'')); 2.46 (td, J ˆ 10.3, 2.4, H C(8')).
13C-NMR (75 MHz, CD3OD): 147.75 (s); 132.76 (2d); 129.24 (s); 123.88 (2d); 102.46 (s); 91.75 (s); 84.22 (s);
81.41 (d); 80.93 (2d); 78.67 (d); 78.01 (d); 76.51 (s); 75.58 (s); 75.56 (d); 75.41 (d); 72.64 (d); 72.61 (d); 70.88 (s);
68.62 (s); 63.63 (t); 63.60 (t); 38.75 (d); 38.25 (d).
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Received November 19, 1998