Reaction of sugar phosphonates with sucrose aldehydes. Synthesis of higher analogs of sucrose

Article abstract of DOI:10.1081/CAR-100105713

The Horner-Emmons reaction between sugar phosphonates Sug-C(O)CH₂ P(O)(OMe)₂ and aldehydes derived from sucrose afforded precursors of higher analogs of the general formula Sug-C(O)CH=CH-Suc. An example of the functionalization of th

Full text of DOI:10.1081/CAR-100105713

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REACTION OF SUGAR PHOSPHONATES WITH SUCROSE
ALDEHYDES. SYNTHESIS OF HIGHER ANALOGS OF
SUCROSE
Mateusz Mach a & Sławomir Jarosz b
a Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52,
Warszawa, 01-224, Poland
b Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52,
Warszawa, 01-224, Poland
Version of record first published: 16 Aug 2006
To cite this article: Mateusz Mach & Sławomir Jarosz (2001): REACTION OF SUGAR PHOSPHONATES WITH SUCROSE
ALDEHYDES. SYNTHESIS OF HIGHER ANALOGS OF SUCROSE, Journal of Carbohydrate Chemistry, 20:5, 411-424
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J. CARBOHYDRATE CHEMISTRY, 20(5), 411–424 (2001)
REACTION OF SUGAR PHOSPHONATES WITH
SUCROSE ALDEHYDES. SYNTHESIS OF HIGHER
ANALOGS OF SUCROSE
Mateusz Mach and Sl⁄awomir Jarosz*
Institute of Organic Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warszawa, Poland
Dedicated to Professor Gerard Descotes on the occasion of his 68th birthday
and for his great achievements in sugar chemistry.
ABSTRACT
The Horner-Emmons reaction between sugar phosphonates Sug-C(O)CH2
P(O)(OMe)2 and aldehydes derived from sucrose afforded precursors of higher
analogs of the general formula Sug-C(O)CHBCH-Suc. An example of
the functionalization of the internal three-carbon saccharide connecting unit is
provided.
INTRODUCTION
Recently we elaborated a convenient methodology for the preparation of su-
crose derivatives having either terminal OH free (at positions C-1ꢀ, C-6 and C-
6ꢀ; compounds 1, 2, and 3, respectively) and in which all secondary hydroxyl
groups were protected as ꢁ easily removable under neutral conditions—benzyl
ethers.1
*Corresponding author. E-mail: sljar@icho.edu.pl
411
Copyright © 2001 by Marcel Dekker, Inc.
www.dekker.com

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Oxidation of either terminal free hydroxyl group to an aldehyde, followed by
reaction with the simplest stabilized ylid (Ph3PBCHCO2Me) and osmylation of
the resulting ꢂ,ꢃ-unsaturated ester, led to higher sucrose analogs elongated by two
carbon atoms.1 This approach might be regarded as an application of a Brima-
combe methodology2 to sucrose chemistry. We reasoned that availability of the
different sucrose aldehydes should also open a convenient route to even higher
derivatives by coupling of sucrose with different monosaccharide sub-units.
RESULTS AND DISCUSSION
Our strategy for the preparation of the sucrose analogs consisted of three ma-
jor steps: i. coupling of sucrose (‘Suc’CH2OH) with simple monosaccharide
(‘Sug’CH2OH) moieties via an additional carbon (‘C1’) atom, ii. functionalization
of the resulting allylic bridge and iii. final deprotection (Fig.1).
The Horner-Emmons methodology was particularly useful for the construc-
tion of a higher sugar skeleton from simple monosaccharides,3,4 and so we decided,
therefore, to apply this reaction to the synthesis of higher analogs of sucrose.
Synthesis of the Higher Sucrose Precursors
The phosphonates 4,4 5,5 6,4 and 76 used in this study, derived from 1,2:3,4-
di-O-isopropylidene-ꢂ-D-galactose, benzyl ꢂ-D-mannoside, L-threo-ꢃ-D-gluco-
octose and sucrose, respectively, were prepared conveniently by reaction of the
corresponding methyl uronates with dimethyl methyl phosphonate anion (Fig. 2).
To check the applicability of the Horner-Emmons methodology in sucrose
chemistry we performed the coupling of all three sucrose aldehydes (1a, 2a, and
Figure 1. Synthetic plan for the preparation of higher analogs of sucrose.

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413
Figure 2. Preparation of sugar phosphonates.
3a; see Scheme 1) with one selected phosphorous reagent, dimethyl (1,2:3,4-di-O-
isopropylidene-ꢂ-D-galacto-heptopyranos-6-ulos-7-yl)phosphonate (4).
Under the mild phase-transfer conditions (K2CO3, 18-crown-6, toluene, room
temp) phosphonate 4 reacted with the corresponding regioisomeric aldehydes
1a–3a to afford all three sucrose derivatives homologated by 7-carbon atoms at the
C-1ꢀ- (8, 61%), C-6 (9, 82%) and C-6ꢀ (10, 86%) positions (Scheme 1). The con-
Scheme 1. i. (COCl)2, DMSO, Et3N; ii. 4, K2CO3, 18 ꢄ crown ꢄ 6, toluene, rt.

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MACH AND JAROSZ
figuration of the newly created double bonds in all these compounds were assigned
as E on the basis of the 1H NMR data (Jolef. ꢀ16 Hz). Enone 8, homologated at the
C-1ꢀ, was obtained in relatively lower yield, since this neo-pentyl-like position is
much less reactive than C-6 and C-6ꢀ.
Having established the usefulness of the phosphonate method for the prepa-
ration of regioisomeric sucrose enones, we concentrated our attention on the ex-
tension of this reaction to other phosphonates.
Phosphonates 5 and 6 reacted with aldehyde 2a (derived from alcohol 2) un-
der the same mild phase-transfer conditions affording the corresponding higher su-
crose enones 11 and 12 in good yields. Moreover, compound 13, regioisomeric to
enone 9, was readily prepared by reaction of sucrose phosphonate 7 and ‘di-
acetonogalactose’ aldehyde.
The enones obtained in this study, together with the previously prepared1
compound 14, represent a wide variety of such modified sucroses (Fig. 3) and are
good evidence of the usefulness of the phosphonate methodology in sucrose chem-
istry.
Functionalization of Selected Higher Sucrose Enone
The next problem to be solved in the synthesis of higher sucrose derivatives
was the functionalization of the allylic bridge connecting the sucrose and the
monosaccharide units. Consequently, we decided to apply a general methodology
we described over the past several years for the transformation of a higher sugar
Figure 3. Different higher sucrose enones prepared by a phosphonate method.

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415
Figure 4. Stereochemistry of the reduction of higher monosaccharide enones of the D-series with
zinc borohydride7.
enone system into a triol moiety. Reduction7 of the carbonyl function of the 2-un-
saturated ketone in such enones (D-series) can be performed with high stereoselec-
tively using zinc borohydride (Fig. 4).
The residual carbon to carbon double bond of the allylic alcohol unit might
then be oxidized conveniently with osmium tetraoxide to the corresponding triol.8
We expected that the above-presented methodology might be also successfully ap-
plied in a functionalization of higher sucrose enones.
Indeed, treatment of the enone 13 with Zn(BH4)2 afforded exclusively allylic
alcohol 15 (Scheme 2) in which the R-configuration at the newly created chiral
center was assigned on the basis of the CD spectral data.1,9 The positive Cotton ef-
fect (at ꢅ 306 nm) observed for a complex of 16 (obtained in two simple steps from
15) with dimolybdenum tetraacetate pointed unequivocally to an R-configuration
at the C-6 position.
Dihydroxylation of a double bond in allylic alcohol 15 would afford a triol,
in which determination of the configuration at the newly created chiral centers
Scheme 2. i. Zn(BH4)2, Et2O, 0 ˚C, 83%; ii. a). O3, CH2Cl2-MeOH, ꢁ78 ˚C; b). NaBH4, 68%;
iii. TBMSCI, DMAP, imidazole, DMF, 90 ˚C, 88%; iv. OsO4 (cat.), NMO.

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MACH AND JAROSZ
Scheme 3. i. a) Na/NH3, -78 ˚C, 30 min; b) Ac2O, Py; ii. H2/Pd/C, AcOH (cat).
might be difficult. We decided, therefore, to protect the free hydroxy group as a
tert-butyldimethylsilyl ether (→ 17), since the configuration of the resulting threo-
diol might be readily determined by CD spectroscopy. Moreover, such protection
should not affect the selectivity of the osmylation resulting from Kishi’s rule.10
Catalytic osmylation of the double bond in compound 17 afforded, however,
both stereoisomeric diols 18 and 19 in a 1:1 ratio (Scheme 2), although both oxy-
gen functions flanking the double bond should act in the same direction. This ob-
servation confirmed our earlier findings1 that such a dihydroxylation is much less
selective in sucrose chemistry than in similar transformations of higher monosac-
charides.
Determination of the configuration at the newly created chiral centers in 18
and 19 was based on the CD spectra of the complexes of both diols with dimolyb-
denum tetraacetate. The positive Cotton effect at ꢅ ꢄ 304.5 nm recorded for a com-
plex of 18 pointed to the 6R,7R configurations while the negative effect at ꢅ
ꢄ 321.5 nm for a complex of 19 proved the 6S,7S geometry at these stereogenic
centers.
The final step in our synthesis of higher sucrose derivatives was deprotection
of the protected sucrose unit. Hydrogenolysis over palladium on charcoal did not
remove the benzyl groups, while the same reaction performed in the presence of
small amounts of acetic acid resulted in hydrolysis of the glycosidic linkage. How-
ever, the benzyl groups, the BOM and TBDPS groups, but not TBDMS group,
were removed with sodium in liquid ammonia. Acetylation of the crude product af-
forded the final compound 20 in 58% overall yield.
CONCLUSIONS
The sucrose molecule was conveniently homologated at either terminal posi-
tion by a Horner-Emmons reaction of the corresponding sugar phosphonates with
aldehydes derived from sucrose, affording enones of general formula Suc-
CHBCH-C(O)-Sug. An alternative version, reaction of the sucrose phosphonate
with a sugar aldehyde was also possible. The three-carbon-atom bridge in each

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417
enone was converted into a triol system by highly stereoselective reduction of the
carbonyl function with zinc borohydride, followed by cis-dihydroxylation of the
double bond. The latter process was completely non-selective (a 1:1 ratio of iso-
meric diols was obtained) in agreement with our earlier observation on the very
low selectivity of osmylation of sucrose derivatives.
The benzyl and benzyloxymethyl alcohol protecting groups on the sucrose
backbone could not be removed by catalytic hydrogenolysis, but were reductively
cleaved with Na/liquid NH3.
EXPERIMENTAL
1H NMR spectra were recorded with a Varian Gemini 200 or Bruker AM 500
spectrometer for solutions in benzene-d6 or CDCl3 (internal Me4Si). Assignments
of the signals were made on the basis of 1H–1H COSY and DEPT 135° experiments
(for numbering of the protons see drawings in the text). Mass spectra (LSIMS; m-
nitrobenzyl alcohol was used as a matrix to which sodium acetate was added) were
recorded with an AMD-604 apparatus. Optical rotations were measured with a
Digital Jasco polarimeter DIP-360 for solutions in CHCl3 (c 1). Column chro-
matography was performed on silica gel (Merck, 70–230 or 230–400 mesh). CD
spectra were measured between 650 and 230 nm at room temperature with a Jasco
J715 spectropolarimeter using DMSO solutions in cells of 0.2 path length (spectral
band width 1 nm, sensitivity 10 ꢆ 10ꢁ6 or 20 ꢆ 10ꢁ6 ꢇA-unit/nm). Depending on
the S/N-ratio the ꢅ-scan speed was 0.2 or 0.5 nm/s. For CD measurements the chi-
ral diol (1–3 mg) was dissolved in a solution of the stock [Mo2(OAc)4] complex
(6–7 mg) in DMSO (10 mL) so that the molar ratio of the stock complex to diol
was about 1:0.3 to 1:0.7. As the true concentrations of the individual optically ac-
tive complexes are not known, apparent ꢇꢈꢀ values are given, calculated from the
total ligand concentration and assuming 100% complexation. [Mo2(OAc)4] and
DMSO (Uvasol) were commercially available from Fluka AG and E. Merck, re-
spectively, and were used without further purification. THF and methylene chlo-
ride were distilled from potassium and calcium hydride, respectively, prior to use.
Dry toluene and diethyl ether were stored over sodium wire. For chromatography
purposes a fraction of mineral oil with boiling point in a range 70–90°C was used
as mixture of hexanes. All solutions were dried over anhydrous sodium sulfate.
Acetylation reactions were performed under standard conditions: acetic anhydride,
TEA, DMAP as a catalyst in dry methylene chloride.
General Procedure for Homologation of Sucrose at Either
Terminal Position
Phosphonate 4, 5, 6 or 7 (1.5 mmol), aldehyde 1a, 2a, or 3a (1.0 mmol, ob-
tained by a Swern oxidation11 of the corresponding alcohol 1, 2, or 3) or 1,2:3,4-
di-O-isopropylidene- ꢂ-D-galactopyranos-6-ulose (for reaction with 7) and 18-

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MACH AND JAROSZ
crown-6 (6.0 mmol) were dissolved in dry toluene (50 mL) to which anhydrous
potassium carbonate (3.0 mmol) was added. The mixture was stirred overnight
at room temperature, water was added and the product was extracted with
ethyl acetate. The organic phase was washed with water and brine, dried,
concentrated and the product was isolated by column chromatography (hexanes
ꢁ ethyl acetate, 6:1 to 2:1). Catalytic amounts of tetrabutylammonium bromide
can also be used instead of 18-crown-6 without significant decrease in product
yields.
2,3,4-Tri-O-benzyl-6-O-p-nitrobenzoyl-ꢀ-D-glucopyranosyl-(1↔9)-(E)-
10,11-di-O-benzyl-7,8-dideoxy-13-O-p-nitrobenzoyl-1,2:3,4-di-O-isopropyli-
dene-ꢁ-D-xylo-D-galacto-trideca-7-en-6,9-diulo-9,12-furanoside (8). (61%);
[ꢂ] ꢉ7.7°; m/z: 1365 [M(C74H74N2O22) ꢉ Naꢉ]. 1H NMR (500 MHz, CDCl3, se-
lected signals) ꢊ 7.07 and 7.00 (AB of H-7f and H-8f, 2H, JAB ꢄ 15.5), 5.55 (d, 1H,
J1,2 ꢄ 5.0 Hz, H-1f), 5.35 (d, 1H, J1,2 ꢄ 3.3 Hz, H-1g), 4.12 ( broad d, 1H, H-5g),
4.00 (dd, 1H, H-3g), 3.51 (dd, 1H, J3,4 ꢄ 9.2 Hz, J4,5 ꢄ 9.9 Hz, H-4g), 3.42 (dd,
1H, J2,3 ꢄ 9.7 Hz, H-2g), 1.43, 1.28, 1.26, 1.17 [4ꢆs, 4ꢆ3H, 2ꢆC(CH3)2]. 13C
NMR (50 MHz, CDCl3) ꢊ 196.5 (C-6f), 164.2, 164.0 [2ꢆp-O2NPhC(O)O], 142.7
(C-8f), 126.5 (C-7f), 109.6, 108.9 [2ꢆC(CH3)2], 104.7 (C-9f), 96.3, 91.8, 88.9,
82.6, 81.7, 79.5, 78.0, 76.8 (8ꢆCH), 75.7, 75.0 (2ꢆCH2), 73.5 (CH), 72.9 (double
intensity), 72.5 (3ꢆCH2), 72.3, 70.5, 70.2, 69.7 (4ꢆCH), 66.1, 63.8 (2ꢆCH2),
25.9, 25.8, 24.7, 24.1 [2ꢆC(CH3)2].
Anal. Calcd for C74H74N2O22: C, 66.16; H, 5.55; N, 2.09. Found: C, 66.4; H,
5.8; N, 2.1.
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructofuranosyl-(2↔1)-(E)-2,3,4-tri-O-benzyl-6,7-dideoxy-10,11:12,13-di-O-
isopropylidene-ꢁ-L-galacto-D-gluco-tridecadialdo-6-en-8-ulo-1,5-pyranoside
1
(9). (82%); [ꢂ] ꢁ0.9°; m/z: 1425 [M(C84H94O17Si) ꢉ Naꢉ]. H NMR, (500
MHz, CDCl3, selected signals) ꢊ 6.93 (dd, 1H, J5,6 ꢄ 4.5 Hz, J6,7 ꢄ 15.8 Hz, H-
6g), 6.77 (dd, 1H, J5,7 ꢄ 1.5 Hz, H-7g), 5.98 (d, 1H, J1,2 ꢄ 3.6 Hz, H-1g), 5.45 (d,
1H, J12,13 ꢄ 5.0 Hz, H-13g), 4.85–4.30 (m, 20H: 6ꢆOCH2Ph, OCH2O, H-5g, H-
3f, H-4f, H-11g, H-10g and H-9g), 4.25 (broad d, 1H, H-12g), 4.02 (dd, 1H, J5,6a
ꢄ 3.5 Hz, J6a,6b ꢄ 11.3 Hz, H-6af), 3.49 (m, 1H, H-5f), 3.90 (dd, 1H, H-3g), 3.87
(dd, 1H, J5,6b ꢄ 4.4 Hz, H-6bf), 3.75 and 3.67 (AB of H-1af and H-1bf, 2H, JAB
ꢄ 11.1 Hz), 4.42 (dd, 1H, J2,3 ꢄ 9.7 Hz, H-2g), 3.17 (dd, 1H, J3,4 ꢄ 9.1 Hz, J4,5
ꢄ 10.0 Hz, H-4g), 1.40, 1.27, 1.23, 1.18 [4ꢆs, 4ꢆ3 H, 2ꢆC(CH3)2], 1.08 [s, 9H,
SiC(CH3)3]. 13C NMR (50 MHz, C6D6) ꢊ 195.8 (C-8g), 144.6 (C-6g), 125.5 (C-
7g), 109.5, 108.6 [2ꢆC(CH3)2], 104.5 (C-2f), 96.9 (CH), 95.0 (OCH2OCH2Ph),
89.1, 84.2, 82.3, 82.2, 81.5, 81.4, 80.3 (7ꢆCH), 75.6, 75.2 (2ꢆCH2), 73.8 (CH),
73.4, 73.1 (2ꢆCH2), 72.8 (CH), 72.5 (CH2), 71.1 (double intensity), 71.0 (3ꢆCH),
70.4, 69.5, 64.8 (3ꢆCH2), 27.3 (SiC(CH3)3), 26.2, 26.0, 24.7, 24.2 [2ꢆC(CH3)2],
19.6 [SiC(CH3)3].
Anal. Calcd for C84H94O17SiꢋH2O: C, 70.96; H 6.81. Found: C, 70.3; H, 6.9.

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2,3,4-Tri-O-benzyl-6-O-t-butyldiphenylsilyl-ꢀ-D-glucopyranosyl-
(1↔12)-(E)-10,11-di-O-benzyl-7,8-dideoxy-13-O-benzyloxymethyl-1,2:3,4-di-
O-isopropylidene-ꢁ-D-lyxo-D-galacto-trideca-7-en-6,12-diulo-9,12-furanoside
1
(10). (86%); [ꢂ] ꢁ1.7°; m/z: 1425 [M(C84H94O17Si) ꢉ Naꢉ]. H NMR, (500
MHz, CDCl3, selected signals) ꢊ 6.98 (dd, 1H, J7,9 ꢄ 1.2 Hz, J7,8 ꢄ 15.7 Hz, H-
7f), 5.67 (d, 1H, J1,2 ꢄ 3.8 Hz, H-1g), 5.51 (d, 1H, J1,2 ꢄ 5.0 Hz, H-1f), 4.43 (ddd,
1H, J8,9 ꢄ 5.9 Hz, H-9f), 4.37 (d, 1H, J10,11 ꢄ 8.4 Hz, H-11f). 4.26 (d, 1H, J2,3
ꢄ 1.2 Hz, H-2f), 4.17 (dd, 1H, J9,10 ꢄ 8.5 Hz, H-10f), 3.77 and 3.68 (AB of H-13af
and H-13bf, 2H, JAB ꢄ 11.2 Hz), 3.65–3.56 (m, 2H, H-2g and H-4g), 1.46, 1.29,
1.27, 1.26 [4ꢆs, 4ꢆ3H, 2ꢆC(CH3)2], 1.00 [s, 9H, SiC(CH3)3]. 13C NMR (50
MHz, C6D6) ꢊ 195.9 (C-6f), 143.7 (C-8f), 126.2 (C-7f), 109.6, 108.8
[2ꢆC(CH3)2], 104.8 (C-12f), 96.8 (CH), 95.0 (OCH2OCH2Ph), 90.2, 85.0, 83.9,
82.7, 81.1, 80.3, 78.1 (7ꢆCH), 75.8, 75.2 (2ꢆCH2), 74.0 (CH), 73.5, 73.2
(2ꢆCH2), 73.1 (CH), 72.6 (CH2), 72.5 71.1, 70.8 (3ꢆCH), 70.0, 69.6,
63.2 (3ꢆCH2), 26.4 [SiC(CH3)3], 25.3, 25.1, 23.8, 23.5 [2ꢆC(CH3)2], 18.8
[SiC(CH3)3].
Anal. Calcd for C84H94O17SiꢋH2O: C, 70.96; H, 6.81. Found: C, 71.0; H, 6.9.
Benzyl (3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-
ꢁ-D-fructofuranosyl)-(2↔1)-(E)-2,3,4,10,11,12-hexa-O-benzyl-6,7-dideoxy-ꢀ-
L-manno-ꢀ-D-gluco-tridecadialdo-6-en-8-ulo-1,5:9,13-dipyranoside (11).
(83%); [ꢂ] ꢉ73.2°; m/z: 1705 [M(C106H110O17Si) ꢉ Naꢉ]. 1H NMR (500 MHz,
CDCl3, selected signals) ꢊ 6.97 (dd, 1H, J5,6 ꢄ 4.7 Hz, J6,7 ꢄ 15.5 Hz, H-6g), 6.78
(dd, 1H, J5,7 ꢄ 1.4 Hz, H-7g), 5.26 (d, 1H, J1,2 ꢄ 3.5 Hz, H-1g), 3.77 and 3.69 (AB
of H-1af and H-1bf, 2H, JAB ꢄ 11.1 Hz), 3.44 (dd, 1H, J2,3 ꢄ 9.6 Hz, H-2g), 3.16
(dd, 1H, J3,4 ꢄ 9.3 Hz, J4,5 ꢄ 9.75 Hz, H-4g), 1.05 [s, 9H, SiC(CH3)3]. 13C NMR
(125 MHz, C6D6) ꢊ 194.5 (C-8g), 145.1 (C-6g), 126.9 (C-7g), 104.7 (C-2f), 98.4
(CH), 94.9 (OCH2OCH2Ph), 89.6, 84.3, 82.2, 82.01, 81.97, 81.7, 80.3, 79.9, 76.8,
76.2 (10ꢆCH), 75.6 (CH2), 75.4 (CH), 74.93, 74.88, 73.4, 73.1, 73.0, 72.6, 72.5
(7ꢆCH2), 71.0 (CH), 70.1, 69.7, 69.6, 65.2 (4ꢆCH2), 27.2 [SiC(CH3)3], 19.5
[SiC(CH3)3].
Anal. Calcd for C106H110O17Si: C, 75.60; H, 6.58. Found: C, 75.7; H, 6.5.
Methyl (3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsi-
lyl-ꢁ-D-fructofuranosyl)-(2↔1)-(E)-2,3,4,12,13,14-hexa-O-benzyl-6,7-
dideoxy-9,10-O-isopropy-lidene-ꢁ-L-threo-L-altro-ꢀ-D-gluco-pentadecadi-
aldo-6-en-8-ulo-1,5:11,15-dipyranoside (12). (85%); [ꢂ] ꢉ33.8°; m/z: 1729
[M(C105H114O19Si) ꢉ Naꢉ]. 1H NMR (500 MHz, CDCl3, selected signals) ꢊ 6.98
(dd, 1H, J5,6 ꢄ 4.1 Hz, J6,7 ꢄ 15.8 Hz, H-6g), 6.85 (dd, 1H, J5,7 ꢄ 1.7 Hz, H-7g),
6.02 (d, 1H, J1,2 ꢄ 3.7 Hz, H-1g), 3.77 and 3.69 (AB of H-1af and H-1bf, 2H, JAB
ꢄ 11.1 Hz), 3.42 (dd, 1H, J2,3 ꢄ 9.7 Hz, H-2g), 3.37 (s, 3H, OCH3), 3.12 (dd, 1H,
J3,4 ꢄ 8.9 Hz, J4,5 ꢄ 10.2 Hz, H-4g), 1.36, 1.12 [C(CH3)2], 1.07 [s, 9H,
SiC(CH3)3]. 13C NMR (125 MHz, CDCl3) ꢊ 199.4 (C-8g), 145.6 (C-6g), 124.2 (C-
7g), 110.4 [C(CH3)2], 104.0 (C-2f), 97.7 (CH), 94.8 (OCH2OCH2Ph), 88.7, 83.9,

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MACH AND JAROSZ
82.7, 81.73, 81.69, 81.1, 80.6, 79.9, 79.8, 79.7, 78.2, 77.5 (12 ꢆ CH), 75.7, 75.6,
75.0, 74.6, 73.3, 73.2, 72.9, 72.1 (8ꢆCH2), 70.1 (CH), 69.91 (CH2), 69.89 (CH),
69.5, 63.8 (2ꢆCH2), 55.0 (OCH3), 27.0 [SiC(CH3)3], 26.4, 26.0 [C(CH3)2], 19.3
[SiC(CH3)3].
Anal. Calcd for C105H114O19SiꢋH2O: C, 73.06; H, 6.77. Found: C, 73.0; H,
6.8.
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructofuranosyl-(2↔1)-(E)-2,3,4-tri-O-benzyl-7,8-dideoxy-10,11:12,13-di-O-
isopropylidene-ꢁ-L-galacto-D-gluco-tridecadialdo-7-en-6-ulo-1,5-pyranoside
1
(13). (70%); [ꢂ] ꢁ14.7°; m/z: 1425 [M(C84H94O17Si) ꢉ Naꢉ]. H NMR (500
MHz, CDCl3, selected signals) ꢊ 6.96 (dd, 1H, J8,9 ꢄ 4.1 Hz, J7,8 ꢄ 15.7 Hz, H-
8g), 6.74 (dd, 1H, J7,9 ꢄ 1.5 Hz, H-7g), 6.00 (d, 1H, J1,2 ꢄ 3.5 Hz, H-1g), 5.45 (d,
1H, J12,13 ꢄ 5.0 Hz, H-13g), 4.53 (dd, 1H, H-11g), 4.37 (ddd, 1H, H-9g), 4.25 (dd,
1H, J11,12 ꢄ 2.4 Hz, H-12g), 4.15 (dd, 1H, J10,11 ꢄ 7.8 Hz, J9,10 ꢄ 2.1 Hz, H-10g),
3.74–3.64 (m, 3H, AB of H-1af and H-1bf, JAB ꢄ 11.1 Hz and H-4g), 3.48 (dd, 1H,
J2,3 ꢄ 9.7 Hz, H-2g), 1.39, 1.27, 1.23, 1.19 [4ꢆs, 4ꢆ3H, 2ꢆC(CH3)2], 1.04 [s, 9H,
SiC(CH3)3]. 13C NMR (50 MHz, C6D6) ꢊ 194.7 (C-6g), 142.9 (C-8g), 109.5, 108.3
(2 ꢆ C(CH3)2), 104.7 (C-2f), 96.7 (CH), 95.0 (OCH2OCH2Ph), 89.7, 83.7, 82.3,
81.7, 81.6, 80.4, 79.5 (7ꢆCH), 75.6, 75.0 (2ꢆCH2), 74.8 (CH), 73.1 (double in-
tensity; 2ꢆCH2), 73.0 (CH), 72.6 (CH2), 71.3 70.8, 68.2 (3ꢆCH), 70.5, 69.5, 64.6
(3ꢆCH2), 27.3 [SiC(CH3)3], 26.3, 26.1, 24.7, 24.4 [2ꢆC(CH3)2], 19.6
[SiC(CH3)3].
Anal. Calcd for C84H94O17Si: C, 71.87; H, 6.75. Found: C, 71.8; H, 6.6.
Functionalization of the Allylic Bridge in Higher Sucrose Enone 13
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructofuranosyl-(2↔1)-(E)-2,3,4-tri-O-benzyl-7,8-dideoxy-10,11:12,13-di-O-
isopropylidene-ꢁ-L-glycero-D-gluco-D-gluco-tridecadialdo-7-en-1,5-pyra-
noside (15). Enone 13 (1.5 g, 1.069 mmol) was dissolved in dry diethyl ether (50
mL) and cooled to 0°C. A solution of zinc borohydride7,12 in diethyl ether was
added until TLC (hexanes ꢁ ethyl acetate, 1:1) showed disappearance of the start-
ing material and formation of a new, more polar product. The reaction mixture was
diluted with ethyl acetate and excess of zinc borohydride was carefully decom-
posed with water. Organic phase was separated, washed with 2% sulfuric acid, then
with aqueous sodium carbonate, water, brine and dried. Column chromatography
(hexanes ꢁ ethyl acetate, from 6:1 to 3:1) gave 15 as the sole product. (1.24 g,
83%); [ꢂ] ꢁ2.3°; m/z: 1427 [M(C84H96O17Si) ꢉ Naꢉ]. 1H NMR (200 MHz, C6D6,
selected signals) ꢊ 6.45–6.20 (m, 3H, H-1g, H-7g and H-8g), 5.55 (d, 1H, J13,12
ꢄ 4.9 Hz, H-13g), 3.34 (broad d, 1H, J6,OH ꢄ 4.2 Hz, OH), 1.43, 1.38 [2ꢆs, 2ꢆ3H,
C(CH3)2], 1.24 [s, 9H, SiC(CH3)3], 1.08, 1.07 [2ꢆs, 2ꢆ3H, C(CH3)2]. 13C
NMR (50 MHz, C6D6) ꢊ 109.2, 108.2 [(2ꢆC(CH3)2], 104.3 (C-2f), 96.9
(OCH2OCH2Ph), 95.0, 88.7, 83.6, 81.1, 81.0, 80.9, 80.2, 79.3 (8ꢆCH), 75.6, 75.0

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SYNTHESIS OF HIGHER ANALOGS OF SUCROSE
421
(2ꢆCH2), 74.8, 74.4 (2ꢆCH), 73.4, 73.3 (2ꢆCH2), 72.6 (CH), 72.4 (CH2), 71.4
70.7, 69.4 (3ꢆCH), 70.9, 69.6, 63.7 (3ꢆCH2), 27.3 [SiC(CH3)3], 26.5, 26.3, 25.0,
24.5 [2ꢆC(CH3)2], 19.6 [(SiC(CH3)3].
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructo-furanosyl-(2↔1)-2,3,4-tri-O-benzyl-D-glycero-ꢀ-D-glucopyranoside
(16). Ozone was passed through a cooled (ꢁ78°C) and vigorously stirred solu-
tion of alcohol 15 (0.150 g, 0.107 mmol) in CH2Cl2/methanol (1:1 v/v, 30 mL) un-
til a blue-green color persisted. Sodium borohydride (50 mg, 1.5 mmol) was added,
and the mixture was allowed to attain room temperature. Water was added, and the
product was extracted with ethyl acetate. The organic phase was washed with wa-
ter, brine, dried, concentrated and the diol 16 was isolated by column chromatog-
raphy (hexanes ꢁ ethyl acetate, from 3:1 to 1:1). (0.086 g, 68%); [ꢂ] ꢉ32.7°; m/z:
1203 [M(C72H80O13Si) ꢉ Naꢉ]. 1H NMR (500 MHz, CDCl3, selected signals) ꢊ
6.05 (d, 1H, J1,2 ꢄ 3.8 Hz, H-1g), 1.07 [s, 9H, SiC(CH3)3]. 13C NMR (125 MHz,
CDCl3) ꢊ 104.0 (C-2f), 94.9 (OCH2OCH2Ph), 88.3 (C-1g), 83.2, 82.0, 80.3, 80.1
(double intensity), 79.0 (6ꢆCH), 75.5, 74.7, 73.2, 72.9 (4ꢆCH2), 72.3 (CH), 72.0
(CH2), 71.4 (CH), 70.3, 69.6, 63.1, 62.9 (4ꢆCH2), 26.9 [SiC(CH3)3], 19.2
(SiC(CH3)3). CD [ꢅ(ꢇꢈꢀ)]: 306.0 (ꢉ0.22), 351.0 (ꢁ0.07) nm.
Anal. Calcd for C72H80O13Si: C, 73.20; H, 6.83. Found: C, 73.0; H, 7.0.
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructofuranosyl-(2↔1)-(E)-2,3,4-tri-O-benzyl-6-O-t-butyldimethylsilyl-7,8-
dideoxy-10,11:12, 13-di-O-isopropylidene-ꢁ-L-glycero-D-gluco-D-gluco-tride-
cadialdo-7-en-1,5-pyranoside (17). Alcohol 15 (0.925 g, 0.658 mmol), DMAP
(40 mg, 0.033 mmol), imidazole (0.180 g, 2.644 mmol.), and t-butyldimethylsi-
lyl chloride (0.120 g, 0.796 mmol) were dissolved in anhydrous DMF (15 mL)
and stirred at 90°C for 2 h. Water was added and the product was extracted with
ethyl acetate. The organic phase was washed with water, brine, dried, concen-
trated and ether 17 was isolated by column chromatography (hexanes ꢁ ethyl ac-
etate from 8:1 to 3:1). (0.8825 g, 88%); [ꢂ] ꢁ3.1°; m/z: 1541 [M(C90H110O17Si2)
ꢉ Naꢉ]. 1H NMR (500 MHz, C6D6, selected signals) ꢊ 6.17 (dd, 1H, J7,8 ꢄ 16.0
Hz, J7,6 ꢄ 6.7 Hz, H-7), 6.08 (dd, 1H, J8,9 ꢄ 7.1 Hz, H-8), 6.02 (d, 1H, J1,2
ꢄ
3.6 Hz, H-1), 5.51 (d, 1H, J13,12 ꢄ 5.0 Hz, H-13), 4.44 (dd, 1H, J10,11 ꢄ 7.8 Hz,
H-11), 4.39 (dd, 1H, H-9), 4.25 (dd, 1H, H-3), 4.14 (dd, 1H, J11,12 ꢄ 2.3 Hz, H-
12), 4.02 (broad s, 2H, H-1ꢀa and H-1ꢀb), 3.95 (broad t, 1H, J3,4 ꢄ J4,5 ꢄ 9.5 Hz,
H-4), 3.82 (dd, 1H, J9,10 ꢄ 1.9 Hz, H-10), 3.59 (dd, 1H, J2,3 ꢄ 9.7 Hz, H-2),
1.41, 1.36 [2ꢆs, 2ꢆ3H, C(CH3)2], 1.20 [s, 9H, SiC(CH3)3], 1.08, 1.07 [2ꢆs,
2ꢆ3H, C(CH3)2], 1.05 [(s, 9H, SiC(CH3)3], 0.18 [s, 6H, Si(CH3)3(CH3)2]. 13C
NMR (50 MHz, C6D6) ꢊ 109.0, 108.2 [2ꢆC(CH3)2], 104.9 (C-2f), 96.7 (CH),
94.9 (OCH2OCH2Ph), 90.3, 84.3, 83.4, 83.0, 82.3, 80.8, 78.4 (7ꢆCH), 75.8
(CH2), 75.7, 75.4 (2ꢆCH), 74.9 (CH2), 74.4 (CH), 73.1, 72.8, 72.7 (3ꢆCH2),
71.3 70.7, 69.1 (3ꢆCH), 70.0, 69.5, 66.4 (3ꢆCH2), 27.26, 26.55 [2ꢆSiC(CH3)3],
26.48, 26.25, 24.9, 24.4 [2ꢆC(CH3)2], 19.6, 18.8 [2ꢆSiC(CH3)3], ꢁ3.97, ꢁ4.03
[SiC(CH3)3(CH3)2].

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MACH AND JAROSZ
Anal. Calcd for C90H110O17Si2ꢋH2O: C, 70.28; H, 7.34. Found: C, 70.2; H,
7.4.
Dihydroxylation of 17. To a solution of 17 (0.8 g, 0.518 mmol) in THF
(8.0 mL), t-butyl alcohol (0.8 mL) and water (0.1 mL) N-methylmorpholine N-ox-
ide (0.160 g, 1.2 mmol) and OsO4 (0.5 mL of a ca 2% solution in t-butyl alcohol)
were added, and the mixture was stirred for 24 hours at room temperature.
Methanol (20 mL) and saturated aqueous sodium hydrogen sulfite (3 mL) were
added and stirring was prolonged for another 1 hour. The reaction mixture was fil-
tered through Celite and the products were extracted with ethyl acetate. The or-
ganic phase was washed with water, brine, dried, concentrated and the products
were separated using preparative HPLC. Retention times for 18 and 19 are 1.98 and
2.42 min, respectively (Shimadzu LC-8A liquid chromatograph, Shimadzu SPD-
6A UV detector, and column from Machery-Nagel: Nucleosil 100-7; phase: hex-
anes ꢁ ethyl acetate, 3:1 with constant flow rate: 4 mL/min).
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructofuranosyl-(2↔13)-10,11,12-tri-O-benzyl-8-O-t-butyldimethylsilyl-
1,2:3,4-di-O-isopropylidene-ꢁ-L-xylo-L-altro-D-galacto-tridecadialdo-9,13-
pyranoside (18). (40%); [ꢂ] ꢁ5.1°; m/z: 1575 [M(C90H112O19Si2) ꢉ Naꢉ]. 1H
NMR (500 MHz, C6D6, selected signals) ꢊ 5.97 (d, 1H, J12,13 ꢄ 3.5 Hz, H-13g),
5.46 (d, 1H, J1,2 ꢄ 4.9 Hz, H-1g), 4.20 (dd, 1H, J2,3 ꢄ 2.3 Hz, H-2g), 3.65 (dd, 1H,
J11,12 ꢄ 9.7 Hz, H-12g), 3.15 (broad s, 1H, OH), 2.92 (broad d, 1H, OH), 1.49, 1.33
[2ꢆs, 2ꢆ3H, C(CH3)2], 1.27, 1.16 [2ꢆs, 2ꢆ9H, 2ꢆSiC(CH3)3], 1.11, 1.06, [2ꢆs,
2ꢆH, C(CH3)2], 0.36, 0.35 [2ꢆs, 2ꢆ3H, 2ꢆSi(CH3)2(CH3)2]. 13C NMR (125
MHz, C6D6) ꢊ 109.1, 108.5 [2ꢆC(CH3)2], 104.3 (C-2f), 96.6 (CH), 94.4
(OCH2OCH2Ph), 90.3, 84.1, 83.7, 82.8, 82.6, 80.6, 78.1, 76.2 (8ꢆCH), 75.5, 74.9,
72.82, 72.79, 72.56 (5ꢆCH2), 71.3, 71.1, 71.0, 70.9, 70.8, 69.7, 69.5 (7ꢆCH),
69.1, 68.9, 67.3 (3ꢆCH2), 27.0, 26.3 [2ꢆSiC(CH3)3], 26.0, 25.8, 24.7, 24.0
[2ꢆC(CH3)2], 19.3, 18.5 [2ꢆSiC(CH3)3], ꢁ3.7, ꢁ4.7 [(SiC(CH3)3(CH3)2]. CD
[ꢅ(ꢇꢈꢀ)]: 304.5 (ꢉ0.14), 352.5 (ꢁ0.02) nm.
Anal. Calcd for C90H112O19Si2: C, 69.56; H, 7.26. Found: C, 69.5; H, 7.2.
3,4-Di-O-benzyl-1-O-benzyloxymethyl-6-O-t-butyldiphenylsilyl-ꢁ-D-
fructofuranosyl-(2↔13)-10,11,12-tri-O-benzyl-8-O-t-butyldimethylsilyl-
1,2:3,4-di-O-isopropylidene-ꢁ-L-xylo-L-gluco-D-galacto-tridecadialdo-9,13-
pyranoside (19). (40%); [ꢂ] ꢁ2.7°; m/z: 1575 [M(C90H112O19Si2) ꢉ Naꢉ]. 1H
NMR (500 MHz, C6D6, selected signals) ꢊ 5.89 (d, 1H, J12,13 ꢄ 3.6 Hz, H-13g),
5.42 (d, 1H, J1,2 ꢄ 4.9 Hz, H-1g), 4.18 (dd, 1H, J2,3 ꢄ 2.4 Hz, H-2g), 3.64 (dd, 1H,
J11,12 ꢄ 9.7 Hz, H-12g), 3.02 (broad d, 1H, OH), 1.89 (broad d, 1H, OH), 1.50,
1.40, 1.19 (3ꢆs, 3ꢆ3H, C(CH3)2], 1.17 [s, 9H, SiC(CH3)3], 1.09 [s, 12H,
SiC(CH3)3 and one of C(CH3)2], 0.28, 0.24 [2ꢆs, 2ꢆ3H, Si(CH3)3(CH3)2]. 13C
NMR (125 MHz, C6D6) ꢊ 108.7, 108.3 [2ꢆC(CH3)2], 104.7 (C-2f), 96.6 (CH),
94.6 (OCH2OCH2Ph), 89.9, 84.1, 83.7, 83.0, 82.3, 80.5, 76.9 (7ꢆCH), 75.5, 75.4
(2ꢆCH2), 73.9 (CH), 72.80, 72.75, 72.46 (3ꢆCH2), 71.3, 71.2, 71.1, 70.9, 70.6

ORDER
REPRINTS
SYNTHESIS OF HIGHER ANALOGS OF SUCROSE
423
(5ꢆCH), 69.31, 69.28 (2ꢆCH2), 68.8, 67.1 (2ꢆCH), 66.5 (CH2), 26.9, 26.4
[2ꢆSiC(CH3)3], 26.2, 26.0, 25.0, 24.2 [2ꢆC(CH3)2], 19.3, 18.5 [2ꢆSiC(CH3)3],
ꢁ3.1, ꢁ5.2 [SiC(CH3)3(CH3)2]. CD [ꢅ(ꢇꢈꢀ)]: 321.5 (ꢁ0.06), 428.5 (ꢉ0.01) nm.
Anal. Calcd for C90H112O19Si2: C, 69.56; H, 7.26. Found: C, 69.8; H, 7.2.
1,3,4,6-Tetra-O-acetyl-ꢁ-D-fructofuranosyl-(2↔13)-6,7,10,11,12-penta-
O-acetyl-8-O-t-butyldimethylsilyl-1,2:3,4-di-O-isopropylidene-ꢁ-L-xylo-L-
gluco-D-galacto-tridecadialdo-9,13-pyranoside (20). Diol 19 (0.180 g, 0.116
mmol) was dissolved in anhydrous THF (10 mL) and liquid ammonia (30 mL) at
ꢁ78°C. During stirring sodium was added in small pieces until deep blue color
persisted for 30 min. Excess sodium was decomposed by addition of solid ammo-
nium chloride and the reaction mixture was allowed to attain room temperature (ca
16 h). After evaporation of ammonia, the reaction mixture was concentrated in vac-
uum and the residue was acetylated. Column chromatography (hexanes ꢁ ethyl ac-
etate, from 4:1 to 1:2) afforded the desired product 20 (0.075 g, 58%); [ꢂ] ꢉ17.9°;
1
m/z: MS: 1145 [M(C49H74O27Si) ꢉ Naꢉ]. H NMR (500 MHz, CDCl3, selected
signals) ꢊ 5.59 (d, 1H, J12,13 ꢄ 3.6 Hz, H-13g), 5.43 (d, 1H, J1,2 ꢄ 5.0 Hz, H-1g),
5.30 (m, 1H, H-5f), 4.80 (dd, 1H, J11,12 ꢄ 10.0 Hz, H-12g), 4.52 (dd, 1H,
J3,4 ꢄ 8.2 Hz, H-3g), 4.43 (m, 1H, H-6af), 4.23 (dd, 1H, J2,3 ꢄ 2.0 Hz, H-2d),
4.05 (a part of AB, 1H, JAB ꢄ 11.9 Hz, H-1bf), 2.18, 2.14, 2.12, 2.10, 2.09,
2.08, 2.07, 2.05, 1.87 [9ꢆs, 9ꢆ3H, 9ꢆC(O)CH3], 1.56, 1.39, 1.28, 1.26
[4ꢆs, 4ꢆ3H, 2ꢆC(CH3)2], 0.93 [s, 9H, SiC(CH3)3], 0.19, 0.18 [2ꢆs, 2ꢆ3H,
2ꢆSi(CH3)3(CH3)2]. 13C NMR (125 MHz, CDCl3) ꢊ 170.4, 170.3, 170.2, 170.01,
169.99, 169.8, 169.7, 169.4, 169.1 [9ꢆOC(O)CH3], 108.7, 108.2 [2ꢆC(CH3)2],
103.9 (C-2f), 95.8, 90.2, 79.0, 75.9, 75.7, 72.5, 71.4, 70.6, 70.50, 70.47, 70.3, 70.2,
69.9, 69.7, 67.7, 67.0 (16ꢆCH), 64.5, 63.6 (2ꢆCH2), 26.2 [SiC(CH3)3], 25.8, 25.7,
24.9, 23.6 [2ꢆC(CH3)2], 20.73, 20.71 (triple intensity), 20.67 (double), 20.63
(double), 20.45 [9ꢆOC(O)CH3], 18.2 [SiC(CH3)3], ꢁ3.1, ꢁ4.9 [SiC(CH3)3-
(CH3)2].
Anal. Calcd for C49H74O27Si: C, 52.40; H, 6.64. Found: C, 52.5; H, 6.6.
ACKNOWLEDGMENTS
This work was supported by the Grant No 3 T09A 119 16 from the Polish
State Committee for Scientific Research.
REFERENCES
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MACH AND JAROSZ
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Received November 27, 2000
Accepted May 2, 2001

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