Convergent syntheses of C(1→3)-linked disaccharides starting from isolevoglucosenone

Article abstract of DOI:10.1016/S0957-4166(99)00492-9

Nucleophilic addition (Nu^-M⁺) to isolevoglucosenone 1 generates enolates stereospecifically (exo face addition) that can be reacted with sugar-derived aldehydes to give C(1→3)-linked disaccharide precursors with high diastereoselectivity. Limitations of the method arising from unfavorable aldolate stability can be overcome by using Et₂AlI as the nucleophile. This leads to products of Baylis-Hillmann condensations. One example is presented and has led to the preparation of 2,3-anhydro-3-C-[(1S)-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulo-pyranose 5. Copyright (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0957-4166(99)00492-9

TETRAHEDRON:
ASYMMETRY
Pergamon
Tetrahedron: Asymmetry 11 (2000) 263–282
Convergent syntheses of C(1→3)-linked disaccharides starting
from isolevoglucosenone
Yao-Hua Zhu, Raynald Demange and Pierre Vogel ∗
Section de Chimie de l’Université de Lausanne, BCH, CH-1015, Lausanne-Dorigny, Switzerland
Received 22 October 1999; accepted 4 November 1999
Abstract
Nucleophilic addition (Nu−M+) to isolevoglucosenone 1 generates enolates stereospecifically (exo face addition)
that can be reacted with sugar-derived aldehydes to give C(1→3)-linked disaccharide precursors with high
diastereoselectivity. Limitations of the method arising from unfavorable aldolate stability can be overcome by using
Et2AlI as the nucleophile. This leads to products of Baylis–Hillmann condensations. One example is presented
and has led to the preparation of 2,3-anhydro-3-C-[(1S)-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulo-
pyranose 5. © 2000 Elsevier Science Ltd. All rights reserved.
1. Introduction
Carbohydrate mimics are potentially useful molecular tools for biology,1 and may become leads
for drug discovery.2 In particular, C-linked disaccharides and oligosaccharides offer the advantage of
being resistant to acidic and enzymatic hydrolysis.3 They are potential inhibitors of glycosidases and
glycosyltransferases.4,5 They represent non-hydrolyzable epitopes.6 Since the first synthesis of β-D-
Glcp-CH2(1→6)-D-Glcp by Rouzaud and Sinaÿ,7 several approaches to C-disaccharides and C-linked
oligosaccharides have been reported.3,8,9 They are invariably multiple-step syntheses which do not always
offer the necessary versatility for wide molecular diversity.10 In a preliminary communication,11 we
have shown that isolevoglucosenone 1 (derived from D-glucose in four steps12) allows nucleophilic
addition on the less hindered face of the bicyclic enone, generating enolates 2 that can react with
1,2:3,4-di-O-isopropylidene-α-D-galactohexodialdo-1,5-pyranose 3 giving the corresponding aldols 4
that were converted into C(1→3)-linked disaccharides with high stereoselectivity (Scheme 1). We present
details of this convergent approach and disclose its application to the synthesis of 5, a new kind of C-
disaccharide in which β-D-glucopyranose is attached at C(3) of 2,3-anhydro-3-gulo-pyranose through a
hydroxymethylene linker.
∗
Corresponding author. Fax: +41 21 692 39 75; e-mail: pierre.vogel@ico.unil.ch
0957-4166/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(99)00492-9
tetasy 3127

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Scheme 1.
2. Synthesis and structural analysis
Oshima and co-workers have shown that conjugate addition of Me2AlSPh to simple enones, followed
by reaction of the aluminum enolates with aldehydes, allows the preparation of the corresponding aldols
in one-pot procedures.13 Me2AlSPh added to isolevoglucosenone 1 at low temperature (−78°C, CH2Cl2),
giving an enolate that reacted with aldehydes 3 and 6 (−95°C, 3 h), afforded the corresponding aluminum
aldolates 7 and 8. The aldolates so-obtained can be reduced in situ with (i-Bu)2AlH (−78°C, CH2Cl2):
after aqueous work-up, the C-disaccharides 9 (60% yield) and 10 (63% yield) were obtained as single
diastereoisomers, respectively. The high diastereoselectivity of these reductions can be interpreted in
terms of steric factors, the less hindered exo face of the bicyclic ketone, probably coordinated to the
aluminum moiety of the aldolate, being attacked by the hydride (Scheme 2). This is in analogy with
Paterson’s LiBH4 reduction of dicyclohexylboron aldolate.14
Scheme 2.
Replacing Me2AlSPh by Me2AlNBn2 led to generation,15 from 1 and 3, of the corresponding C-
glycoside of protected D-galactosamine 12 (40% yield) which was characterized as its diacetate 13
(Scheme 2). When using Et2AlNBn2 instead of Me2AlNBn2,16 the yield of 12 dropped to 24%.
With Me2AlN(Ac)Bn (prepared by addition of Me3Al to benzyl isocyanate),17 no C-disaccharide was
obtained. The reaction of 1 with 3 with Me2AlN(SiMe3)Bn,18 followed by treatment with (i-Bu)2AlH,
failed to produce a C-disaccharide, probably because Me2AlN(SiMe3)Bn is able to undergo facile
1,2-addition with generation of the corresponding imines that are reduced with (i-Bu)2AlH into the
corresponding N-alkyl-N-benzylamines. This hypothesis is supported by our observation that 14, the
adduct of benzyl alcohol to isolevoglucosenone, reacted with Me2AlN(SiMe3)Bn (CH2Cl2, −78°C) and
then with (i-Bu)2AlH (CH2Cl2, −78°C) affording a 1.1:1 mixture of benzylamines 15 and 16 (52% yield).

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
265
Under the same conditions, 14 reacted with Me2AlNBn2 and then with (i-Bu)2AlH giving a mixture of
alcohols 17 and 18 (56% yield) (Scheme 3). In the latter case, Me2AlNBn2 cannot generate a benzyl
imine resulting from a 1,2-addition to the ketone.
Scheme 3.
The one-pot synthesis of C-disaccharides (Scheme 2) could not be applied to prepare C-glycosides
of D-galactose itself (Nu=OR) as the reaction of 1 with 3 with Me2AlOBn (prepared by the addition of
Me3Al to BnOH in CH2Cl2 at 0°C), followed by reduction with (i-Bu)2AlH, failed to produce any trace
of products of coupling between 1 and 3. The lithium enolate 19 of ketone 14, obtained on treatment with
1 equivalent of (Me3Si)2NLi (THF, −78°C), did not eliminate lithium benzylate at low temperature and
could be reacted with aldehyde 3 (and other aldehydes11) at −95°C, affording a single aldol 20 that could
be isolated in 79% yield. Its reduction with NaBH4 (MeOH/THF, 0°C) was less stereoselective than the
reductions of the aluminum aldolates 7, 8 and 11 with (i-Bu)2AlH (Scheme 4). It gave a 5:1 mixture of
diols 21 (75% yield) and 22 (15% yield).
Scheme 4.
The relative configuration of the hydroxy group of the hydroxymethylene linker and that at C(4) of
the D-galactose moiety of 9, 12 and 21 were established by 1H NMR of their acetonides 23, 24 and 25,
respectively (Fig. 1), obtained on treatment with (MeO)2CMe2/acetone/pTsOH/Drierite. The pyranose
ring of the 1,6-anhydro-D-galactose units of 23 and 25 adopts chair conformations, whereas a boat
conformation is preferred in the case of 24. The NOESY 1H NMR spectrum of 23 showed cross-peaks
for a signal pair at δH=3.95 (H-20)/4.38 ppm (Hendo-60), on the one hand, and for a signal pair at δH=4.08
(H-6)/4.38 ppm (Hendo-60), on the other. The trans relationship between protons H-30 and H-6 was proven
by 3J(H-30, H-6)=9.1 Hz. The observation of 3J(H-30, H-40)=9.1 Hz, 3J(H-20, H-30)=3.0 Hz and 3J(H-
3
40, H-50)=6.1 Hz proved the galacto configuration. Smaller values (<2 Hz) for J(H-40, H-50) would
have been expected if this system had the gluco configuration. The 1H NMR data for 25 were similar to
those for 23, 3J(H-30, H-6)=10.3 Hz and NOEs between H-20(3.84 ppm)/Hendo-60 (4.36 ppm), H-6 (4.44
ppm)/Hendo-60 (4.36 ppm) were observed. The NOESY 1H NMR spectrum of 24 showed a strong NOE
between proton pair H-20 (3.02 ppm)/Hendo-60 (4.23 ppm). Such NOE was not observed for 23 and 25,
in agreement with the boat conformation of the galacto pyranoside moiety of 24. NOEs between proton
pairs Mea (1.31 ppm)/H-5 (3.95 ppm), Mea/H-40 (4.45 ppm), Meb (1.04 ppm)/H-20 (3.02 ppm), Meb/H-6
(4.30 ppm) and H-6/Hendo-60 (4.23 ppm) were also observed. The trans relationship of H-20 and H-30
was given by 3J(H-20, H-30)=10.0 Hz.
The high diastereoselectivity observed for the cross-aldol reactions reported above can be interpreted
in terms of steric factors that make the face of the intermediate enolate (e.g. 19) anti with respect to the

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Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
Fig. 1.
substituent at C(2) more accessible than the syn face (exo face of the bicyclo[3.2.1]octane system) for
the aldehydes. With aluminum and lithium enolates, ‘closed transition states’ are preferred over ‘open
transition states’, and for steric reasons, lead to aldol following the Zimmermann–Traxler model 26 (Fig.
2).19
Fig. 2.
Under the same conditions of Scheme 4, the cross-aldolization of the lithium enolate 19 with the β-
glucopyranose-derived carbaldehyde 2720 led to a mixture of products that was reduced with (i-Bu)2NH
affording less than 7% of the desired C-disaccharide, the other products deriving from the reduction of
ketone 14 and aldehyde 27. This failure is not explained yet. No better success was attained with our
one-pot method (Scheme 2) using Me2AlSPh with 1 and 27. Therefore, we explored the possibility of
carrying out a condensation between 1 and 27 analogous to the Baylis–Hillmann reaction.21
When Et2AlI (1 M in toluene) was added to a mixture of 1 and 27 (CH2Cl2, −95°C),13 the product
of coupling 28 was obtained in 80% yield. Treatment of enone 28 with t-BuOOH (CH2Cl2, DBU,
20°C) afforded epoxide 29 as single product (82% yield). Its relative configuration was given by the
3
relatively small coupling constant J(H-1, H-2)=1.3 Hz. Thus, the less sterically hindered exo face of
the bicyclo[3.2.1]octenone moiety was preferred for the epoxidation (1,4-addition, elimination). The
configuration of the hydroxymethylene linker will be established as shown below. Reduction of ketone
29 with NaBH4 in MeOH (0°C) also prefers the exo face of the bicyclic system, producing alcohol 30 in
95% yield. Debenzylation of 30 with Na/NH3 at −78°C provided hexol 31 in 83% yield. Hydrolysis of
the 1,6-anhydrohexose appeared to be a difficult operation with 31. We thus protected it as polyacetate 32
under standard conditions (Ac2O, pyridine, DMAP, 25°C, 95% yield). Treatment of 32 with CF3COOH in
Ac2O led to a mixture of peracetate 33 (single α-anomer, 37%) and β-pyranose 34 (38%), together with
unreacted starting material 32 (16%). Methanolysis of 33 (NH3/MeOH, 20°C) afforded C-disaccharide
5 (single β-pyranose) in 45% yield after chromatographic purification (Scheme 5).
The configurations of the hydroxymethylene linker and of the 4-hydroxy group in 30–34 (and 5) were
established in the following way. Treatment of 30 with (MeO)2CMe2, acetone and pTsOH as catalyst
produced the corresponding acetonide 35 in 82% yield. Debenzylation of 35 with Na/NH3 in THF
(−78°C) afforded 36 (75% yield), the NOESY 1H NMR spectrum of which showed cross-peaks for the

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
267
Scheme 5.
proton pairs H-10 (4.61 ppm)/Hendo-6 (4.23 ppm), H-10/Mea (1.42 ppm), Meb (1.51 ppm)/H-4 (4.29 ppm),
Mea/H-30 (3.36 ppm) and H-2 (2.99 ppm)/H-20 (2.95 ppm) consistently with the conformation shown for
3
3
36 (Fig. 3). The latter was confirmed by the coupling constants J(H-1, H-2)=1 Hz, J(H-10, H-20) '0
Hz. As for the aldol condensations of Schemes 2 and 4, a closed transition state (Zimmermann–Traxler
model) similar to 26 is adopted for reaction 1+Et2AlI+27→28 (Scheme 5). Distinction between α- and
3
β-anomers for the gulo-pyranoses 5, 34 and pyranoside 33 was based on their J(H-1, H-2) and, in
1
the case of 5, on the NOESY H NMR spectra, and by comparison with data reported for other 2,3-
anhydropyranosides.22
Fig. 3.
3. Conformational analysis of 5
The 600 MHz 1H NMR spectrum of 5 (CD3OD) was recorded at several temperatures between −20
and +60°C. Changes in δH of 5 (versus CHD2OD) were insignificant. The largest variation was 0.06 ppm
observed for H-4. The coupling constants 3J(H-10, H-20)=2.0 Hz and 3J(H-4, H-5)=3.6 Hz did not vary
between −20 and +60°C. We can therefore conclude that 5 adopts a major half-chair conformation for the
anhydro-gulo-pyranose moiety and a major staggered conformation about σ(C-10, C-20). The NOESY
1H NMR (600 MHz, CD3OD, 303 K) of 5 showed significant cross-peaks for proton signals assigned to

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Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
H-1 (5.25 ppm) and H-4 (4.26 ppm). This proves the β-pyranose and the half-chair conformation shown
in Fig. 4. This was confirmed by the observation of an NOE between signals assigned to H-10 (4.53 ppm)
and Hb-6 (3.02 ppm) and by the absence of cross-peak for signals attributed to H-1 and H-5 (3.96 ppm).
Fig. 4.
The strong NOEs observed between signals assigned to H-20 (3.58 ppm), H-60 (3.32 ppm), and H-4
demonstrates that the most stable staggered configuration of the C-disaccharide maintains antiperiplanar
bonds for σ(C-10, C-3)/σ(C-20, C-30) and for σ(C-10, C-20)/σ(C-2, C-3) as predicted by Kishi and co-
workers23 for related C-linked disaccharides. These conclusions were further confirmed by the non-
observation of NOEs between signals assigned to H-30, H-40, H-50, Ha-70, Hb-70 and signals assigned
3
to H-1, H-2, H-4, H-5, Ha-6, Hb-6, and by the fact that the coupling constant J(H-10, H-20)=2.0 Hz,
meaning that the value of the corresponding dihedral angle is not far from 90° (Fig. 5).
Fig. 5.
4. Conclusion
The Oshima coupling of enone and aldehydes has been applied to isolevoglucosenone and sugar-
derived aldehydes. It allows generation of (1→3)-C-linked disaccharides in a few synthetic steps with
high stereoselectivity. Unfortunately, the method is not general yet as the yield depends strongly on the
nature of the aluminum reagent and of the aldehyde. In order to avoid retro-aldolization, a fast elimination
generating 3-substituted isolevoglucosenone can be useful (Baylis–Hillmann type of condensation). An
example has been described using Et2AlI to induce the coupling. It has allowed the preparation of 2,3-

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
269
anhydro-3-C-[(1S)-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulopyranose (5), a β-C-(1→3)-
glucopyranoside of a 2,3-anhydrohexopyranose.
5. Experimental
5.1. General
See Ref. 4. 1H NMR assignments were confirmed by 2D-COSY and NOESY spectra.
5.2. (6R)-6-C-[1,6-Anhydro-3-deoxy-2-S-phenyl-2-thio-β-D-galacto-pyranos-3-yl]-1,2:3,4-di-O-
isopropylidene-α-D-galacto-pyranose 9
Me3Al (2 M solution in toluene, 100 µL, 0.20 mmol) was added to a solution of PhSH (20 µL, 0.20
mmol) in 0.1 mL of CH2Cl2 at 0°C. After 30 min, the mixture was cooled to −78°C and a 0.5 M CH2Cl2
solution of isolevoglucosenone 112 (400 µL, 0.20 mmol) was added. Stirring was continued for 1 h. THF
(0.5 mL) was added and the mixture was cooled to −95°C. A solution of 1,2:3,4-di-O-isopropylidene-α-
D-galactohexodialdo-1,5-pyranose 324 (54 mg, 0.21 mmol) in THF (0.2 mL) was added and the resulting
solution was stirred for 3 h. A CH2Cl2 solution of (i-Bu)2AlH (1 M, 400 µL, 0.40 mmol) was added
dropwise. The mixture was slowly warmed to 20°C and stirred for 1 h, and then quenched with aq.
NH4Cl solution. A 2 M HCl solution (1 mL) was added to dissolve the gel. The aq. phase was extracted
with CH2Cl2. The combined organic phases were dried (Na2SO4) and concentrated in vacuo. The residue
was chromatographed on silica gel (3:7, EtOAc:light petroleum ether) to afford a colorless oil (59 mg,
1
60%): [α]25589=−45, [α]25577=−47, [α]25546=−53, [α]25435=−89, [α]25405=−107 (c 0.4, CHCl3); H
NMR (400 MHz, CDCl3): δ 7.49–7.43, 7.35–7.29, 7.28–7.23 (m, 5H, Ph), 5.62 (s, H-10), 5.54 (d, 3J(H-1,
H-2)=5.1 Hz, H-1), 4.67 (t, 3J(H-40, H-50)=3J(H-30, H-40)=6.6 Hz, H-40), 4.59 (dd, 3J(H-40, H-50)=6.6
3
3
3
Hz, J(H-50, Hexo-60)=4.8 Hz, H-50), 4.54 (dd, J(H-3, H-4)=7.9 Hz, J(H-4, H-5)=2.1 Hz, H-4), 4.52
3
3
2
3
(dd, J(H-3, H-4)=7.9 Hz, J(H-2, H-3)=2.7 Hz, H-3), 4.38 (d, J=7.6 Hz, Hendo-60), 4.32 (dd, J(H-1,
H-2)=5.1 Hz, J(H-2, H-3)=2.7 Hz, H-2), 4.11 (dd, J(H-5, H-6)=7.9 Hz, J(H-6, H-30)=1.8 Hz, H-6),
3
3
3
3.94 (dd, 3J(H-5, H-6)=7.9 Hz, 3J(H-4, H-5)=2.1 Hz, H-5), 3.52 (dd, 2J=7.6 Hz, 3J(H-50, Hexo-60)=4.8
Hz, Hexo-60), 3.38 (d, 3J(H-20, H-30)=7.9 Hz, H-20), 2.23 (m, H-30), 1.54, 1.46, 1.34, 1.32 (4s, 4 Me); 13
C
NMR (100.6 MHz, CDCl3): δ 134.1, 131.8, 129.2, 127.2 (Ph), 109.6, 108.8 (C(O)2Me2), 103.4 (C10),
96.6 (C1), 74.8 (C5), 71.3 (C4), 70.8 (C6, C3), 70.3 (C2), 67.0 (C5), 66.9 (C4), 62.8 (C60), 49.1 (C20),
38.2 (C30), 25.9, 25.9, 24.9, 24.4 (4 Me); CI-MS (NH3): m/z 497 ([M+H]+, 9), 496 (M+·, 2), 449 (11),
448 (16), 432 (13), 277 (10), 250 (11), 85 (67), 83 (100).
5.3. 1,6-Anhydro-3-deoxy-3-[(5R)-1,2-O-isopropylidene-3-O-methyl-α-D-xylo-furanos-5-C-yl]-2-S-
phenyl-2-thio-β-D-galacto-pyranose 10
Me3Al (2 M solution in toluene, 100 µL, 0.20 mmol) was added to a solution of PhSH (20 µL, 0.20
mmol) in 0.1 mL of CH2Cl2 at 0°C. After 30 min, the mixture was cooled to −78°C, to which a 0.5 M
CH2Cl2 solution of 1 (400 µL, 0.20 mmol) was added. Stirring was continued for 1 h. THF (0.5 mL) was
added and the mixture was cooled to −95°C. A solution of 1,2-O-isopropylidene-3-O-methyl-α-D-xylo-
pentodialdo-1,4-furanose 6 (42 mg, 0.21 mmol) in THF (0.2 mL) was added and the resulting solution
was stirred for 3 h. A CH2Cl2 solution of (i-Bu)2AlH (1 M, 400 µL, 0.40 mmol) was added dropwise. The
mixture was slowly warmed to 20°C and stirred for 1 h. It was then quenched with aq. NH4Cl solution.

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Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
A 2 M HCl solution (1 mL) was added to dissolve the gel. The aq. phase was extracted with CH2Cl2. The
combined organic phases were dried (Na2SO4) and concentrated in vacuo. Chromatography on silica gel
(2:3, EtOAc:light petroleum ether) afforded a white solid (55 mg, 63%): mp 178–180°C; [α]25589=−38,
[α]25577=−39, [α]25546=−44, [α]25435=−76, [α]25405=−89 (c 1.77, CHCl3); UV (CH3CN): λmax 252
1
(ε=7720), 196 (15810); IR (KBr): ν 3163, 1385, 1376, 1217, 1166, 1114, 1075, 1058, 1028 cm−1; H
NMR (400 MHz, CDCl3): δ 7.44–7.21 (m, 5H, Ph), 5.91 (d, 3J(H-10, H-20)=4.0 Hz, H-10), 5.58 (s, H-1),
5.11 (d, 3J(OH, H-4)=4.3 Hz, OH), 4.67-4.59 (m, 2H, H-4, 50), 4.57 (dd, 3J(H-4, H-5)=5.5 Hz, 3J(H-5,
Hexo-6)=4.8 Hz, H-5), 4.57 (d, 3J(H-10, H-20)=4.0 Hz, H-20), 4.32 (d, 2J=7.7 Hz, Hendo-6), 4.20 (dd, 3J(H-
3
3
2
40, H-50)=6.3 Hz, J(H-30, H-40)=3.3 Hz, H-40), 3.86 (d, J(OH, H-50)=7.0 Hz, OH), 3.59 (dd, J=7.7
Hz, J(H-5, Hexo-6)=4.8 Hz, Hexo-6), 3.56 (d, J(H-30, H-40)=3.3 Hz, H-30), 3.43 (d, J(H-2, H-3)=5.6
Hz, H-2), 3.37 (s, OCH3), 2.30 (ddd, 3J(H-50, H-3)=6.8 Hz, 3J(H-3, H-4)=6.3 Hz, 3J(H-2, H-3)=5.6 Hz,
H-3) 1.46, 1.32 (2s, 2 Me); 13C NMR (100.6 MHz, CDCl3): δ 134.2, 132.0, 129.3, 127.5 (Ph), 111.6
(C(O)2Me2), 104.8 (C10), 102.5 (C1), 84.8 (C30), 80.7 (C20), 79.6 (C40), 75.4 (C5), 71.1 (C50), 67.3
(C4), 63.3 (C6), 57.4 (OMe), 49.5 (C2), 41.3 (C3), 26.8, 26.1 (2 CH3); CI-MS (NH3): m/z 441 ([M+H]+,
7), 440 (M+·, 7), 383 (4), 323 (8), 203 (7), 173 (17), 165 (14), 164 (24), 110 (100), 109 (36); anal. calcd
for C21H28O8S: C, 57.25; H, 6.41; found: C, 57.17; H, 6.50.
3
3
3
5.4. (6R)-6-O-Acetyl-6-C-[4-O-acetyl-1,6-anhydro-2-dibenzylamino-2,3-dideoxy-β-D-galacto-pyranos-
3-yl]-1,2:3,4-di-O-isopropylidene-α-D-galacto-pyranose 13
To a solution of Bn2NH (38 µL, 0.20 mmol) in 0.1 mL of CH2Cl2 was added Me3Al (2 M solution
in toluene, 100 µL, 0.20 mmol) at 0°C. The mixture was warmed to 20°C and stirred for 30 min. After
being cooled down to −78°C, a 0.5 M CH2Cl2 solution of 1 (400 µL, 0.20 mmol) was added. Stirring
was continued for 1 h. THF (0.5 mL) was added and the mixture was cooled to −95°C. A solution of 3
(54 mg, 0.21 mmol) in THF (0.2 mL) was added and the resulting solution was stirred for 3 h. A CH2Cl2
solution of (i-Bu)2AlH (1 M, 400 µL, 0.40 mmol) was added dropwise. The mixture was slowly warmed
to 20°C and stirred for 1 h, and then quenched with a 6 M aq. NaOH solution (0.5 mL) at 0°C. The
mixture was stirred at 20°C for 2 h. The aq. phase was extracted with CH2Cl2. The combined organic
phases were dried (Na2SO4) and concentrated in vacuo. Chromatography on silica gel (3:7, EtOAc:light
petroleum ether) afforded a colorless oil (72 mg, containing 46 mg of pure 12, 40%).
Data for 12: 1H NMR (400 MHz, CDCl3): δ 7.40–7.20 (m, 5H, Ph), 5.71 (s, H-10), 5.54 (d, 3J(H-1, H-
2)=5.2 Hz, H-1), 4.68 (dd, 3J(H-3, H-4)=7.9 Hz, 3J(H-2, H-3)=2.4 Hz, H-3), 4.60 (dd, 3J(H-40, H-50)=7.9
Hz, 3J(H-50, Hexo-60)=4.5 Hz, H-50), 4.54 (m, H-6), 4.39 (dd, 3J(H-40, H-50)=7.9 Hz, 3J(H-30, H-40)=2.1
3
3
3
Hz, H-40), 4.34 (dd, J(H-1, H-2)=5.2 Hz, J(H-2, H-3)=2.4 Hz, H-2), 4.27 (dd, J(H-3, H-4)=7.9 Hz,
3J(H-4, H-5)=1.5 Hz, H-4), 4.00 (dd, 3J(H-5, H-6)=10.0 Hz, 3J(H-4, H-5)=1.5 Hz, H-5), 3.90 (d, 2J=13.6
Hz, PhCH2), 3.84 (d, 2J=6.7 Hz, Hendo-60), 3.51 (d, 2J=13.3 Hz, PhCH2), 3.36 (dd, 2J=6.7 Hz, 3J(H-50,
Hexo-60)=4.5 Hz, Hexo-60), 2.81 (d, J(H-20, H-30)=11.2 Hz, H-20), 2.08 (ddd, J(H-20, H-30)=11.2 Hz,
3
3
3J(H-6, H-30)=6.1 Hz, 3J(H-30, H-40)=2.1 Hz, H-30), 1.63, 1.56, 1.44, 1.33 (4s, 4 Me).
To a CH2Cl2 solution (1 mL) of the above product (0.079 mmol) were added Ac2O (0.10 mL, 1.06
mmol), Et3N (0.20 mL, 1.44 mmol) and DMAP (1 mg, 0.008 mmol). The mixture was stirred at 20°C
for 5 h and concentrated in vacuo. Chromatography (3:7, EtOAc:light petroleum ether) afforded 13
(47 mg, 89%) as a white solid: mp 80–82°C; [α]25589=6.1, [α]25577=4.4, [α]25546=4.8, [α]25435=7.3,
[α]25405=8.5 (c 0.75, CHCl3); UV (CH3CN): λmax 260 (ε=1290), 208 (14190); IR (KBr): ν 3028, 2987,
1744, 1454, 1382, 1257, 1212, 1106, 1068 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.40–7.20 (m, 10H),
5.57 (s, H-10), 5.54 (d, 3J(H-1, H-2)=5.5 Hz, H-1), 5.44 (dd, 3J(H-40, H-50)=8.2 Hz, 3J(H-30, H-40)=6.4
Hz, H-40), 4.92 (dd, 3J(H-40, H-50)=8.2 Hz, 3J(H-50, Hexo-60)=4.5 Hz, H-50), 4.65 (dd, 3J(H-3, H-4)=7.9

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
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3
3
3
Hz, J(H-2, H-3)=2.1 Hz, H-3), 4.62 (m, H-6), 4.45 (dd, J(H-3, H-4)=7.9 Hz, J(H-4, H-5)=1.8 Hz,
H-4), 4.34 (dd, 3J(H-1, H-2)=5.5 Hz, 3J(H-2, H-3)=2.1 Hz, H-2), 3.94 (d, 2H, 2J=13.6 Hz, PhCH2), 3.67
(dd, 3J(H-5, H-6)=9.7 Hz, 3J(H-4, H-5)=1.8 Hz, H-5), 3.64 (d, 2J=8.2 Hz, Hendo-60), 3.57 (d, 2H, 2J=13.6
Hz, PhCH2), 3.36 (dd, 2J=8.2 Hz, 3J(H-50, Hexo-60)=4.5 Hz, Hexo-60), 3.12 (d, 3J(H-20, H-30)=11.2 Hz,
H-20), 2.29 (ddd, J(H-20, H-30)=11.2 Hz, J(H-30, H-40)=6.4 Hz, J(H-6, H-30)=3.0 Hz, H-30), 2.05,
2.03 (2s, 2 CH3CO), 1.59, 1.44, 1.42, 1.32 (4s, 4 Me); 13C NMR (100.6 MHz, CDCl3): δ 170.1, 139.2,
129.2, 128.1, 127.0, 108.8, 108.2, 100.2, 96.4, 72.1, 70.8, 70.4, 70.3, 67.4, 66.9, 62.4, 60.4, 58.8, 32.8,
26.2, 25.8, 24.6, 24.5, 21.1, 21.0; CI-MS (NH3): m/z 626 (7), 610 (10), 534 (9), 280 (8), 253 (11), 252
(58), 91 (100); anal. calcd for C36H45O11N: C, 64.75; H, 6.79; N, 2.10; found: C, 64.25; H, 6.84; N,
2.17.
3
3
3
5.5. 1,6-Anhydro-2-O-benzyl-3-deoxy-D-erythro-hexopyrano-4-ulose 14
A mixture of 1 (185 mg, 1.47 mmol), benzyl alcohol (8.2 mL) and Et3N (0.10 mL, 1.0 mmol) was
stirred at 20°C for 15 h. Et3N was then eliminated by evaporation. Excess of BnOH was recovered by
bulb-to-bulb distillation in vacuo. Chromatography on silica gel (15:85, EtOAc:light petroleum ether)
afforded a colorless syrup (310 mg, 90%): [α]25589=−57, [α]25577=−58, [α]25546=−67, [α]25435=−133,
[α]25405=−176 (c 1.2, CHCl3); UV (CH3CN): λmax 207 (ε=9444), 194 (13480); IR (film): ν 3032, 2899,
1736, 1497, 1455, 1133, 1095, 999 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.45–7.22 (m, 5H, Ph), 5.62
2
3
2
(s, H-1), 4.63, 4.57 (2d, J=12.0 Hz, PhCH2), 4.55 (d, J(H-5, Hexo-6)=5.0 Hz, H-5), 3.92 (d, J=8.0
2
3
3
Hz, Hendo-6), 3.84 (dd, J=8.0 Hz, J(H-5, Hexo-6)=5.0 Hz, Hexo-6), 3.78 (ddd, J(H-2, H-3b)=6.5 Hz,
3J(H-2, H-3a)=3.5 Hz, 3J(H-2, H-1)=1.2 Hz, H-2), 2.68 (dd, 2J=12.5 Hz, 3J(H-2, H-3b)=6.5 Hz, H-3b),
2.61 (dd, J=12.5 Hz, J(H-2, H-3a)=3.5 Hz, H-3a); 13C NMR (100.6 MHz, CDCl3): δ 204.1 (s, C4),
2
3
1
1
137.2 (s, Ph), 128.6, 128.1, 127.7 (3d, J=160 Hz, Ph), 101.5 (d, J(C, H)=175 Hz, C1), 79.1 (d, J(C,
H)=161 Hz, C5), 75.5 (d, 1J(C, H)=146 Hz, C2), 71.6 (t, 1J(C, H)=142 Hz, C6), 66.8 (t, 1J(C, H)=155
Hz, PhCH2), 39.2 (t, 1J(C, H)=131 Hz, C3); CI-MS (NH3): m/z 253 (16), 252 (18, [M+NH4]+), 170 (8),
126 (61), 108 (47), 105 (22), 97 (25), 91 (100), 83 (41); anal. calcd for C13H14O4: C, 66.66; H, 6.02;
found: C, 66.56; H, 6.01.
5.6. 4-Amino-1,6-anhydro-2-O,4-N-dibenzyl-3,4-dideoxy-β-D-xylo-hexopyranose 15 and 4-amino-1,6-
anhydro-2-O,4-N-dibenzyl-3,4-dideoxy-β-D-ribo-hexopyranose 16
A 2 M heptane solution of Me3Al (120 µL, 0.235 mmol) was added dropwise to a CH2Cl2 solution
(0.2 mL) of Bn(TMS)NH (50 µL, 0.235 mmol) at 20°C. After 30 min, the mixture was cooled to −78°C
and a solution of 14 (50 mg, 0.214 mmol) in 0.3 mL of CH2Cl2 was added dropwise. Stirring was
continued for 1 h and (i-Bu)2AlH (400 µL, 0.40 mmol) was added dropwise. The reaction mixture was
stirred at −78°C for 2 h and quenched by careful addition of 6 M NaOH (2 mL). The mixture was stirred
vigorously for 30 min and extracted with CH2Cl2. The organic extract was washed with brine, dried
(Na2SO4) and concentrated. Chromatography (1:1, EtOAc:light petroleum ether, then EtOAc) afforded
colorless oils 15 (19 mg, 27%) and 16 (17 mg, 25%).
Data for 15: [α]25589=−41, [α]25577=−40, [α]25546=−46, [α]25435=−81, [α]25405=−97 (c 0.90,
CHCl3); UV (CH3CN): λmax 263 (ε=880), 258 (890), 251 (870), 212 (8660); IR (film): ν 2957, 2895,
1
1494, 1454, 1365, 1142, 1096, 1061, 1027, 987 cm−1; H NMR (400 MHz, CDCl3): δ 7.42–7.24 (m,
10H, Ph), 5.36 (s, H-1), 4.63, 4.54 (2d, 2J=11.6 Hz, PhCH2), 4.40 (m, H-5), 4.08 (d, 2J=7.7 Hz, Hendo
-
2
2
3
6), 3.84, 3.77 (2d, J=12.3 Hz, PhCH2), 3.65 (dd, J=7.7 Hz, J(H-5, Hexo-6)=5.1 Hz, Hexo-6), 3.43
3
3
3
3
(dd, J(H-2, H-3a)=4.4 Hz, J(H-2, H-3e)=1.6 Hz, H-2), 3.30 (ddd, J(H-3a, H-4)=11.9 Hz, J(H-3e,

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3
2
3
3
H-4)=5.6 Hz, J(H-4, H-5)=3.5 Hz, H-4), 1.98 (ddd, J=14.0 Hz, J(H-3e, H-4)=5.6 Hz, J(H-2, H-
3e)=1.6 Hz, H-3e), 1.48 (ddd, J=14.0 Hz, J(H-3a, H-4)=11.9 Hz, J(H-2, H-3a)=4.4 Hz, H-3a); 13C
NMR (100.6 MHz, CDCl3): δ 141.5, 136.7, 128.5, 128.4, 127.9, 127.7, 127.7, 127.1 (Ph), 99.8 (C1),
74.7, 74.1, 71.4, 63.1, 51.7, 51.5, 28.6; CI-MS (NH3): m/z 326 (26, [M+H]+), 282 (4), 252 (10), 234 (3),
175 (5), 133 (15), 106 (45), 91 (100); anal. calcd for C20H23O3N: C, 73.82, H, 7.12; N, 4.30; found: C,
73.78; H, 7.17; N, 4.29.
2
3
3
Data for 16: [α]25589=−47, [α]25577=−47, [α]25546=−54, [α]25435=−90, [α]25405=−107 (c 0.75,
CHCl3); UV (CH3CN): 263 (1620), 212 (7730); IR (film): ν 2953, 2892, 1494, 1454, 1146, 1118, 1062,
1024, 923 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.45–7.22 (m, 10H, Ph), 5.44 (s, H-1), 4.67 (dd, 3J(H-
5, Hexo-6)=5.4 Hz, 3J(H-5, Hendo-6)=0.9 Hz, H-5), 4.65 and 4.57 (2d, 2J=12.3 Hz, PhCH2), 3.89 (s, 2H,
PhCH2), 3.85 (dd, 2J=7.2 Hz, 3J(H-5, Hexo-6)=5.4 Hz, Hexo-6), 3.81 (dd, 2J=7.2 Hz, 3J(H-5, Hendo-6)=0.9
Hz, Hendo-6), 3.40 (dd, 3J(H-2, H-3a)=4.6 Hz, 3J(H-2, H-3e)=2.1 Hz, H-2), 2.60 (dd, 3J(H-3a, H-4)=5.4
Hz, 3J(H-3e, H-4)=1.5 Hz, H-4), 2.23 (br s, NH), 2.07 (ddd, 2J=15.4 Hz, 3J(H-2, H-3e)=2.1 Hz, 3J(H-3e,
2
3
3
H-4)=1.5 Hz, H-3e), 1.88 (ddd, J=15.4 Hz, J(H-3a, H-4)=5.4 Hz, J(H-2, H-3a)=4.6 Hz, H-3a); 13C
NMR (100.6 MHz, CDCl3): δ 140.8, 136.7, 128.4, 128.3, 128.1, 127.7, 127.7, 126.8 (Ph), 100.6 (C1),
75.1, 73.5, 71.4, 66.4, 53.1, 50.5, 24.0; CI-MS (NH3): m/z 326 (20, [M+H]+), 282 (4), 252 (10), 234 (3),
219 (3), 191 (6), 175 (4), 133 (16), 106 (46), 91 (100); anal. calcd for C20H23O3N: C, 73.82; H, 7.12; N,
4.30; found: C, 73.78; H, 7.12; N, 4.26.
5.7. 1,6-Anhydro-2-O-benzyl-3-deoxy-β-D-xylo-hexopyranose 17 and 1,6-anhydro-2-O-benzyl-
3-deoxy-β-D-ribo-hexopyranose 18
A 2 M heptane solution of Me3Al (90 µL, 0.183 mmol) was added dropwise to a CH2Cl2 solution
(0.2 mL) of Bn2NH (35 µL, 0.183 mmol) at 20°C. After 30 min, the mixture was cooled to −78°C and
a solution of 14 (39 mg, 0.167 mmol) in 0.3 mL of CH2Cl2 was added dropwise. Stirring was continued
for 1 h and (i-Bu)2AlH (310 µL, 0.312 mmol) was added dropwise. The reaction mixture was stirred at
−78°C for 2 h and quenched by careful addition of 6 M NaOH (2 mL). The mixture was stirred vigorously
for 30 min and extracted with CH2Cl2. The organic extract was washed with brine, dried (Na2SO4) and
concentrated in vacuo. Chromatography (2:3, EtOAc:light petroleum ether) afforded a colorless oil (22
mg, 56%, 17:18=1.1:1):25 1H NMR (400 MHz, CDCl3): δ 7.42–7.22 (m, 5H, Ph), 5.44 (s, 0.48H, H-1
of 18), 5.35 (s, 0.52H, H-1 of 17), 4.65, 4.47 (2d, 2J=12.4 Hz, 0.96H, PhCH2 of 18), 4.63 and 4.54 (2d,
2J=12.4 Hz, 1.04H, PhCH2 of 17), 4.52 (m, 0.48H, H-5 of 18), 4.37 (m, 0.52H, H-5 of 17), 4.22 (ddd,
3J(H-3a, H-4)=10.9 Hz, 3J(H-3e, H-4)=5.5 Hz, 3J(H-4, H-5)=3.9 Hz, 0.52H, H-4 of 17), 4.08 (d, 2J=7.6
Hz, 0.52H, Hendo-6 of 17), 3.83 (dd, 2J=7.6 Hz, 3J(H-5, Hexo-6)=4.8 Hz, 0.48H, Hexo-6 of 18), 3.78 (dd,
2J=7.6 Hz, 3J(H-5, Hendo-6)=1.2 Hz, 0.48H, Hendo-6 of 18), 3.50 (dd, 2J=7.6 Hz, 3J(H-5, Hexo-6)=5.1 Hz,
0.52H, Hexo-6 of 17), 3.63 (m, 0.48H, H-4 of 18), 3.47 (dd, 3J(H-2, H-3a)=4.5 Hz, 3J(H-2, H-3e)=1.5 Hz,
0.52H, H-2 of 17), 3.45 (m, 0.48H, H-2 of 18), 2.11 (ddd, 2J=14.2 Hz, 3J(H-3e, H-4)=5.5 Hz, 3J(H-2, H-
3e)=1.5 Hz, 0.52H, H-3e of 17), 1.96 (m, 0.96H, H-3 of 18), 1.59 (ddd, 2J=14.2 Hz, 3J(H-3a, H-4)=10.9
Hz, 3J(H-2, H-3a)=4.5 Hz, 0.52H, H-3a of 17).
5.8. (6R)-6-C-[1,6-Anhydro-2-O-benzyl-3-deoxy-β-D-xylo-hexopyrano-4-ulos-3-yl]-1,2:3,4-di-O-iso-
propylidene-α-D-galacto-pyranose 20
A solution of nBuLi in hexane (1.6 M, 280 µL, 0.450 mmol) was added dropwise to a stirred solution
of (Me3Si)2NH (140 µL, 0.654 mmol) in THF (0.6 mL) at −10°C. After 20 min, the mixture was cooled
to −78°C and a solution of 14 (90 mg, 0.385 mmol) in THF (1 mL) was added dropwise over a period

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
273
of 30 min. At the end of the addition, the mixture was left at −78°C for 30 min then cooled to −95°C.
A solution of 3 (130 mg, 0.504 mmol) in THF (0.5 mL) was added dropwise and the mixture was stirred
at −95°C for 3.5 h before a 10% solution of AcOH in THF (20 mL) was added dropwise at −78°C.
After being warmed up to −10°C, the mixture was quenched with a saturated aq. solution of NaHCO3
(15 mL) and extracted with CH2Cl2 (20 mL, three times). The combined organic phases were dried over
Na2SO4 and concentrated in vacuo. Chromatography on silica gel (2:3, EtOAc:light petroleum ether)
afforded a white solid (150 mg, 79%): 1H NMR (400 MHz, CDCl3): δ 7.37–7.24 (m, 5H, Ph), 5.66 (s,
H-10), 5.46 (d, 3J(H-1, H-2)=4.8 Hz, H-1), 4.71 (d, 2J=11.8 Hz, PhCH2), 4.64 (dd, 3J(H-3, H-4)=7.9 Hz,
3J(H-2, H-3)=2.7 Hz, H-3), 4.60 (d, 2J=11.8 Hz, PhCH2), 4.51 (d, 3J(H-50, Hexo-60)=5.1 Hz, H-50), 4.47
(dd, 3J(H-3, H-4)=7.9 Hz, 3J(H-4, H-5)=1.8 Hz, H-4), 4.30 (dd, 3J(H-1, H-2)=4.8 Hz, 3J(H-2, H-3)=2.7
3
3
3
Hz, H-2), 4.27 (dd, J(H-5, H-6)=9.7 Hz, J(H-6, H-30)=1.5 Hz, H-6), 3.95 (dd, J(H-5, H-6)=9.7 Hz,
3J(H-4, H-5)=1.8 Hz, H-5), 3.84 (d, J=7.6 Hz, Hendo-60), 3.68 (dd, J=7.6 Hz, J(H-50, Hexo-60)=5.1
Hz, Hexo-60), 3.60 (d, 3J(H-20, H-30)=7.0 Hz, H-20), 3.23 (dd, 3J(H-20, H-30)=7.0 Hz, 3J(H-6, H-30)=1.5
Hz, H-30), 1.51, 1.44, 1.35, 1.28 (4s, 4 CH3); 13C NMR (100.6 MHz, CDCl3): δ 210.5 (s, C40), 137.3
(s, Ph), 128.3 (d, 1J(C, H)=158 Hz, Ph), 127.8 (d, 1J(C, H)=158 Hz, Ph), 109.2, 108.7 (2s, 2 Me2C(O)2),
102.5 (d, 1J(C, H)=177 Hz, C10), 96.3 (d, 1J(C, H)=178 Hz, C1), 78.4 (d, 1J(C, H)=162 Hz, C3), 78.3
(d, 1J(C, H)=149 Hz, C20),72.1 (t, 1J(C, H)=143 Hz, PhCH2), 70.6 (d, 1J(C, H)=157 Hz, C50), 70.5 (d,
1J(C, H)=152 Hz, C2), 67.6 (d, 1J(C, H)=146 Hz, C4, C6), 67.2 (d, 1J(C, H)=144 Hz, C5), 60.3 (t, 1J(C,
H)=147 Hz, H-60), 49.7 (d, 1J(C, H)=128 Hz, C30), 25.9, 25.5, 24.9, 24.5 (4q, 1J(C, H)=127 Hz, 4 Me).
2
2
3
5.9. (6R)-6-C-(1,6-Anhydro-2-O-benzyl-3-deoxy-β-D-galacto-pyranos-3-yl)-1,2:3,4-di-O-isopropyl-
idene-α-D-galacto-pyranose 21 and (6R)-6-C-[1,6-anhydro-2-O-benzyl-3-deoxy-β-D-galacto-pyranos-
3-yl]-1,2:3,4-di-O-isopropylidene-α-D-gluco-pyranose 22
NaBH4 (11 mg, 0.30 mmol) was added to a stirred solution of 20 (49 mg, 0.10 mmol) in 1:1
THF:MeOH (3 mL) at 0°C. After 0.5 h at 0°C, the reaction mixture was quenched with a saturated
aq. solution of NH4Cl. The aq. phase was extracted with CH2Cl2 (10 mL, three times). The combined
organic phases were dried (Na2SO4) and concentrated. Chromatography on silica gel (1:1, EtOAc:light
petroleum ether) afforded white solids 21 (37 mg, 75%) and 22 (7 mg, 15%).
Data for 21: mp 155–156°C; [α]25589=−27, [α]25577=−29, [α]25546=−33, [α]25435=−56,
[α]25405=−66 (c 0.65, CHCl3); IR (KBr): ν 3283, 2989, 1455, 1384, 1260, 1213, 1065, 1003
1
3
cm−1; H NMR (400 MHz, CDCl3): δ 7.43–7.29 (m, 5H), 5.56 (d, J(H-1, H-2)=5.1 Hz, H-1), 5.47
(s, H-10), 4.72, 4.53 (2d, J=11.8 Hz, PhCH2), 4.67–4.58 (m, 3H, H-3, H-40, H-50), 4.42 (dd, J(H-3,
2
3
3
3
3
H-4)=7.9 Hz, J(H-4, H-5)=1.8 Hz, H-4), 4.35 (dd, J(H-1, H-2)=5.1 Hz, J(H-2, H-3)=2.4 Hz, H-2),
4.34 (d, J=7.6 Hz, Hendo-60), 4.25 (dd, J(H-5, H-6)=8.5 Hz, J(H-6, H-30)=4.5 Hz, H-6), 3.98 (dd,
2
3
3
3J(H-5, H-6)=8.5 Hz, J(H-4, H-5)=1.8 Hz, H-5), 3.53 (d, J(H-20, H-30)=8.2 Hz, H-20), 3.46 (dd,
3
3
2J=7.6 Hz, J(H-50, Hexo-60)=4.5 Hz, Hexo-60), 2.18 (m, H-30), 1.54, 1.49, 1.37, 1.34 (4s, 4 Me); 13C
3
1
1
NMR (100.6 MHz, CDCl3): δ 137.9 (s, Ph), 128.5 (d, J(C, H)=159 Hz, Ph), 128.1 (d, J(C, H)=158
1
1
Hz, Ph), 127.9 (d, J(C, H)=158 Hz, Ph), 109.5, 108.7 (2s, 2 C(O)2Me2), 102.0 (d, J(C, H)=177 Hz,
C10), 96.5 (d, J(C, H)=179 Hz, C1), 77.1 (d, J(C, H)=145 Hz, C20), 73.9 (d, J(C, H)=156 Hz, C3),
71.6 (t, 1J(C, H)=155 Hz, PhCH2), 71.0 (d, 1J(C, H)=150 Hz, C4), 70.8 (d, 1J(C, H)=152 Hz, C50), 70.4
(d, 1J(C, H)=154 Hz, C2), 70.1 (d, 1J(C, H)=147 Hz, C6), 67.6 (d, 1J(C, H)=141 Hz, C5), 65.3 (d, 1J(C,
H)=148 Hz, C40), 61.9 (t, 1J(C, H)=150 Hz, C60), 38.7 (d, 1J(C, H)=131 Hz, C30), 26.0, 25.9, 24.9, 24.6
1
1
1
(4q, J(C, H)=125 Hz, 4 Me); CI-MS (NH3): m/z 512 ([M+NH4]+, 15), 496 (10), 495 ([M+H]+, 25),
1
479 (5), 277 (18), 276 (19), 100 (33), 91 (100); anal. calcd for C25H34O10: C, 60.72; H, 6.93; found: C,
60.85; H, 6.95.

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1
3
Data for 22: H NMR (400 MHz, CDCl3): δ 7.42–7.22 (m, 5H, Ph), 5.58 (d, J(H-1, H-2)=5.1 Hz,
H-1), 5.50 (s, H-10), 4.68 (d, 2J=11.9 Hz, PhCH2), 4.62 (dd, 3J(H-3, H-4)=7.8 Hz, 3J(H-2, H-3)=2.4 Hz,
H-3), 4.57 (d, 2J=11.9 Hz, PhCH2), 4.56 (d, 3J(H-50, Hexo-60)=5.4 Hz, H-50), 4.43 (dd, 3J(H-3, H-4)=7.8
3
3
3
Hz, J(H-4, H-5)=1.9 Hz, H-4), 4.35 (dd, J(H-1, H-2)=5.1 Hz, J(H-2, H-3)=2.4 Hz, H-2), 3.97 (m,
H-6), 3.81 (dd, 3J(H-5, H-6)=8.1 Hz, 3J(H-4, H-5)=1.9 Hz, H-5), 3.80 (d, 3J(H-30, H-40)=4.9 Hz, H-40),
3.74 (d, 2J=7.6 Hz, Hendo-60), 3.70 (dd, 2J=7.6 Hz, 3J(H-50, Hexo-60)=5.4 Hz, Hexo-60), 3.25 (d, 3J(H-20,
H-30)=5.4 Hz, H-20), 2.19 (dt, 3J(H-20, H-30)=5.4 Hz, 3J(H-30, H-40)=3J(H-6, H-30)=4.9 Hz, H-30), 1.54,
1.47, 1.37, 1.33 (4s, 4 Me).
5.10. Acetonide 23
A mixture of 9 (62 mg, 0.137 mmol), 2,2-dimethoxypropane (0.6 mL), Drierite (3 g), dry acetone
(3 mL) and pTsOH (1 mg) was stirred at 20°C for 9 h. Et3N (0.3 mL) was added and the solid was
then filtered off. The filtrate was evaporated in vacuo. Chromatography on silica gel (8:92, EtOAc:light
petroleum ether) afforded a colorless oil (35 mg, 48%): [α]25589=−69, [α]25577=−78, [α]25546=−85,
[α]25435=−146, [α]25405=−168 (c 0.17, CHCl3); UV (CH3CN): λmax 255 (ε=5040), 202 (8176); IR
1
(film): ν 2986, 2935, 1378, 1255, 1215, 1132, 1069, 1002 cm−1; H NMR (400 MHz, CDCl3): δ
7.58–7.53, 7.31–7.19 (m, 5H, Ph), 5.53 (d, 3J(H-1, H-2)=5.2 Hz, H-1), 5.27 (s, H-10), 4.57 (dd, 3J(H-3,
H-4)=7.9 Hz, 3J(H-2, H-3)=2.4 Hz, H-3), 4.50 (dd, 3J(H-40, H-50)=6.1 Hz, 3J(H-50, Hexo-6)=5.1 Hz, H-
50), 4.45–4.38 (m, 3H, H-40, 60endo, 4), 4.28 (dd, 3J(H-1, H-2)=5.2 Hz, 3J(H-2, H-3)=2.4 Hz, H-2), 4.08
(dd, 3J(H-6, H-30)=9.1 Hz, 3J(H-5, H-6)=8.5 Hz, H-6), 3.95 (d, 3J(H-20, H-30)=3.0 Hz, H-20), 3.88 (dd,
3J(H-5, H-6)=8.5 Hz, 3J(H-4, H-5)=1.5 Hz, H-5), 3.58 (dd, 2J=7.6 Hz, 3J(H-50, Hexo-60)=5.1 Hz, Hexo
-
60), 2.25 (dt, 3J(H-6, H-30)=3J(H-30, H-40)=9.1 Hz, 3J(H-20, H-30)=3.0 Hz, H-30), 1.53, 1.47, 1.39, 1.35,
1
1.34, 1.29 (6s, 6 Me); 13C NMR (100.6 MHz, CDCl3): δ 134.5 (s, Ph), 131.9, 128.8, 127.0 (3d, J(C,
H)=160 Hz, Ph), 108.8, 108.7 (2s, C(O)2Me2), 102.1 (d, 1J(C, H)=178 Hz, C10), 100.2 (s, C(O)2Me2),
96.1 (d, 1J(C, H)=180 Hz, C1), 73.1 (d, 1J(C, H)=157 Hz, C50), 70.7 (d, 1J(C, H)=151 Hz, C2), 70.5 (d,
1
1
1
1J(C, H)=155 Hz, C40), 70.4 (d, J(C, H)=154 Hz, C3), 70.1 (d, J(C, H)=136 Hz, C5), 68.7 (d, J(C,
H)=145 Hz, C6), 63.8 (t, 1J(C, H)=152 Hz, C60), 63.3 (d, 1J(C, H)=151 Hz, C4), 45.5 (d, 1J(C, H)=147
Hz, C20), 40.7 (d, J(C, H)=133 Hz, C30), 27.6, 26.1, 26.0, 25.4, 25.0, 24.4 (6q, J=125 Hz, 6 Me);
CI-MS (NH3): m/z 538 (44), 537 ([M+H]+, 100), 536 (M+·, 33), 479 (9), 430 (8), 429 (10), 370 (8), 320
(5), 81 (17); anal. calcd for C27H36O9S: C, 60.43; H, 6.76; found: C, 60.41; H, 6.88.
1
1
5.11. Acetonide 24
A mixture of 12 (41 mg, 0.071 mmol), 2,2-dimethoxypropane (1 mL), Drierite (1 g, powder), dry
acetone (2 mL) and pTsOH (1 mg) was stirred at 20°C for 6 h. K2CO3 (10 mg) was added and the
solid was then filtered off. The filtrate was evaporated in vacuo. Chromatography on silica gel (8:92,
EtOAc:light petroleum ether) afforded a colorless oil (28 mg, 64%): [α]25589=−39, [α]25577=−41,
[α]25546=−47, [α]25435=−78, [α]25405=−93 (c 1.4, CHCl3); UV (CH3CN): λmax 258 (ε=913), 213
(7724); IR (film): ν 2986, 1376, 1214, 1072, 997 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.44–7.18 (m,
5H, Ph), 5.54 (s, H-10), 5.28 (d, 3J(H-1, H-2)=5.2 Hz, H-1), 4.63 (dd, 3J(H-3, H-4)=7.9 Hz, 3J(H-2, H-
3)=2.4 Hz, H-C3), 4.62 (m, H-C50), 4.45 (dd, 3J(H-40, H-50)=8.2 Hz, 3J(H-30, H-40)=4.8 Hz, H-40), 4.42
(dd, 3J(H-3, H-4)=7.9 Hz, 3J(H-4, H-5)=1.8 Hz, H-4), 4.30 (dd, 3J(H-5, H-6)=9.7 Hz, 3J(H-6, H-30)=3.3
Hz, H-6), 4.27 (dd, 3J(H-1, H-2)=5.2 Hz, 3J(H-2, H-3)=2.4 Hz, H-2), 4.23 (d, 2J=6.7 Hz, Hendo-60), 3.98
2
3
3
2
(d, J=13.6 Hz, PhCH2), 3.95 (dd, J(H-5, H-6)=9.7 Hz, J(H-4, H-5)=1.8 Hz, H-5), 3.53 (d, J=13.6
Hz, PhCH2), 3.34 (dd, 2J=6.7 Hz, 3J(H-50, Hexo-60)=4.8 Hz, Hexo-60), 3.02 (d, 3J(H-20, H-30)=10.0 Hz,

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275
3
3
3
H-20), 2.03 (ddd, J(H-20, H-30)=10.0 Hz, J(H-30, H-40)=4.8 Hz, J(H-6, H-30)=3.3 Hz, H-30), 1.65,
1.54, 1.40, 1.31, 1.28, 1.04 (6s, 6 Me); 13C NMR (100.6 MHz, CDCl3): δ 139.5 (s, Ph), 129.2, 128.0,
126.7 (3d, J(C, H)=160 Hz, Ph), 108.9, 108.2 (2s, C(O)2Me2), 99.9 (d, J(C, H)=169 Hz, C10), 98.3
1
1
1
1
1
(s, C(O)2Me2), 96.2 (d, J(C, H)=177 Hz, C1), 72.3 (d, J(C, H)=161 Hz, C3), 70.7 (d, J(C, H)=151
Hz, C50), 70.7 (d, 1J(C, H)=144 Hz, C4), 70.6 (d, 1J(C, H)=152 Hz, C2), 68.3 (d, 1J(C, H)=148 Hz, C5,
C6), 62.8 (d, J(C, H)=151 Hz, C40), 61.9 (t, J(C, H)=153 Hz, C60), 60.7 (d, J(C, H)=137 Hz, C20),
1
1
1
53.5 (t, J(C, H)=132 Hz, PhCH2), 29.6 (d, J(C, H)=129 Hz, C30), 27.8, 26.3, 26.0, 25.6, 24.8, 24.2
(6q, 1J(C, H)=125 Hz, 6 Me); CI-MS (NH3): m/z 624 ([M+H]+, 4), 623 (M+·, 3), 608 ([M–Me]+, 5), 532
([M–PhCH2]+, 8), 464 (8), 281 (13), 252 (29), 251 (10), 236 (12), 91 (100); anal. calcd for C35H45NO9:
C, 67.40; H, 7.27; found: C, 67.40; H, 7.20.
1
1
5.12. Acetonide 25
A mixture of 21 (22 mg, 0.044 mmol), 2,2-dimethoxypropane (0.2 mL), Drierite (1 g), dry acetone (1.6
mL) and pTsOH (0.4 mg) was stirred at 20°C for 4 h. Et3N (0.1 mL) was added and the solid was filtered
off. The filtrate was evaporated in vacuo. Chromatography (1:9, EtOAc:petroleum ether) afforded white
needles (12 mg, 50%): mp 158–160°C; [α]25589=−64, [α]25577=−66, [α]25546=−75, [α]25435=−123,
[α]25405=−146 (c 0.55, CHCl3); UV (CH3CN): λmax 257 (ε=456), 251 (436), 208 (5650); IR (KBr): ν
2984, 2933, 1381, 1372, 1260, 1252, 1244, 1225, 1178, 1169, 1119, 1096, 1074, 1065, 1054 cm−1; 1H
3
NMR (400 MHz, CDCl3): δ 7.42–7.37, 7.35–7.29, 7.28–7.22 (m, 5H, Ph), 5.55 (d, J(H-1, H-2)=5.2
2
2
Hz, H-1), 5.39 (s, H-10), 4.75 (d, J=11.5 Hz, PhCH2), 4.58 and 4.56 (2d, J=11.5 Hz, PhCH2), 4.57
(dd, J(H-3, H-4)=8.2 Hz, J(H-2, H-3)=2.4 Hz, H-3), 4.54–4.47 (m, 2H, H-50, 40), 4.43 (dd, J(H-3,
H-4)=8.2 Hz, 3J(H-4, H-5)=1.8 Hz, H-4), 4.36 (d, 2J=7.3 Hz, Hendo-60), 4.28 (dd, 3J(H-1, H-2)=5.2 Hz,
3J(H-2, H-3)=2.4 Hz, H-2), 4.04 (dd, 3J(H-6, H-30)=10.3 Hz, 3J(H-5, H-6)=8.8 Hz, H-6), 3.85 (dd, 3J(H-
5, H-6)=8.8 Hz, 3J(H-4, H-5)=1.8 Hz, H-5), 3.84 (d, 3J(H-20, H-30)=2.7 Hz, H-20), 3.56 (dd, 2J=7.6 Hz,
3J(H-50, Hexo-60)=4.8 Hz, Hexo-60), 2.38 (ddd, 3J(H-6, H-30)=10.3 Hz, 3J(H-30, H-40)=9.1 Hz, 3J(H-20,
H-30)=2.7 Hz, H-30), 1.47, 1.42, 1.40, 1.35, 1.34, 1.28 (6s, 6 Me); 13C NMR (100.6 MHz, CDCl3): δ
3
3
3
1
138.9 (s, Ph), 128.1, 127.6, 127.3 (3d, J(C, H)=160 Hz, Ph), 108.8, 108.5 (2s, C(O)2Me2), 100.8 (d,
1J(C, H)=173 Hz, C10), 99.8 (s, C(O)2Me2), 96.3 (d, 1J(C, H)=183 Hz, C1), 75.9 (d, 1J(C, H)=148 Hz,
C20), 72.6 (d, 1J(C, H)=157 Hz, C50), 71.4 (t, 1J(C, H)=141 Hz, PhCH2), 71.0 (d, 1J(C, H)=140 Hz, C5),
70.6 (d, 1J(C, H)=152 Hz, C2), 70.4 (d, 1J(C, H)=150 Hz, C4), 70.4 (d, 1J(C, H)=154 Hz, C3), 67.9 (d,
1J(C, H)=145 Hz, C6), 63.3 (t, J(C, H)=155 Hz, C60), 62.8 (d, J(C, H)=149 Hz, C40), 41.9 (d, J(C,
H)=133 Hz, C30), 27.2, 26.1, 26.0, 25.6, 24.9, 24.5 (6q, 1J(C, H)=125 Hz, 6 Me); CI-MS (NH3): m/z 536
(35), 535 ([M+H]+, 78), 519 (7, [M−Me]+), 428 (9), 427 (9), 376 (6), 385 (5), 91 (100); anal. calcd for
C28H38O10: C, 62.92; H, 7.16; found: C, 63.32; H, 7.21.
1
1
1
5.13. 1,6-Anhydro-3-C-[(1S)-2,6-anhydro-3,4,5,7-tetra-O-benzyl-D-glycero-D-gulo-heptitol-1-C-yl]-2,
3-dideoxy-β-D-glycero-hex-2-en-4-ulopyranose 28
1 M Et2AlI in toluene (5.3 mL, 5.3 mmol) was added dropwise in 45 min to a stirred solution of
2720 (2.36 g, 4.3 mmol) and 1 (0.65 g, 5.1 mmol) in anhydrous CH2Cl2 (16 mL) cooled to −95°C
under Ar atmosphere. After stirring at −95°C for 4 h, the cooling bath was removed and Et2O (50
mL), then 1 M aq. HCl (6 mL) were added under vigorous stirring (red mixture becomes yellowish).
After the addition of H2O (50 mL), the aqueous phase was extracted with Et2O (50 mL, three times). The
combined org. phases were washed with brine (50 mL) and dried (MgSO4). Solvent evaporation and flash
chromatography on silica gel (3:1, light petroleum ether:EtOAc) afforded 2.32 g (80%) of white solid: mp

276
Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
113–114°C (EtOH); [α]25589=+45.3, [α]25577=+48.3, [α]25546=+67.4, [α]25435=+289, [α]25405=+706 (c
0.1, CHCl3); UV (MeCN): λmax 244 (ε=7000), 217 (11500); IR (KBr): ν 3415, 2865, 1695, 1495, 1455,
1355, 1100, 1060, 735, 700 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.38–7.12 (m, 20H), 7.07 (dd, 3J(H-
4
3
2, H-1)=3.5, J(H-2, H-10)=1.5 Hz, H-2), 5.78 (d, J(H-1, H-2)=3.5 Hz, H-1), 4.96-4.74 (m, 5H), 4.63
(dd, 3J(H-5, Hexo-6)=6.2, 3J(H-5, Hendo-6)=1.2 Hz, H-5), 4.58 (br s, H-10), 4.53–4.39 (m, 3H), 3.91 (dd,
2J=8.2, 3J(Hexo-6, H-5)=6.2 Hz, Hexo-6), 3.83 (t, 3J(H-30, H-40)=3J(H-30, H-20)=9.1 Hz, H-30), 3.73 (t,
3J(H-40, H-50)=3J(H-40, H-30)=9.1 Hz, H-40), 3.64 (dd, 3J(H-20, H-30)=9.1, 3J(H-20, H-10)=1.8 Hz, H-
20), 3.59 (d, 3J(H-70, H-60)=3.4 Hz, H2C(70)), 3.55 (dd, 2J=8.2, 3J(Hendo-6, H-5)=1.2 Hz, Hendo-6), 3.52
3
3
3
(t, J(H-50, H-60)=3J(H-50, H-40)=9.1 Hz, H-50), 3.34 (dt, J(H-60, H-50)=9.1, J(H-60, H-70)=3.4 Hz,
H-60); 13C NMR (100.6 MHz, CDCl3): δ 194.5 (s, C-4), 142.3 (d, 1J(C, H)=166 Hz, C-2), 138.4, 138.1,
138.0, 137.9, 137.7 (5s), 128.4-127.8 (20d), 96.8 (d, 1J(C, H)=177 Hz, C-1), 86.9 (d, 1J(C, H)=141 Hz,
C-40), 79.2 (d, 1J(C, H)=167 Hz, C-5), 78.6 (2d, 1J(C, H)=141, C-2, 1J(C, H)=139 Hz, C-20, C-60), 78.0
1
1
1
(d, J(C, H)=138 Hz, C-50), 77.6 (d, J(C, H)=137 Hz, C-30), 75.4, 74.9, 74.8, 73.3 (4t, J(C, H)=142
Hz, CH2 (Bn)), 69.2 (t, 1J(C, H)=142 Hz, C-70), 65.9 (d, 1J(C, H)=146 Hz, C-10), 62.1 (t, 1J(C, H)=151
Hz, C-6); CI-MS (NH3): m/z 697 (0.2, [M+18]+), 663 (0.4), 441 (0.9), 256 (11.3), 191 (3.9), 91 (100);
anal. calcd for C41H42O9 (678.77): C, 72.55; H, 6.24; found: C, 72.64; H, 6.25.
5.14. 1,6:2,3-Dianhydro-3-C-[(1S)-2,6-anhydro-3,4,5,7-tetra-O-benzyl-D-glycero-D-gulo-heptitol-1-C-
yl]-β-D-ribo-hex-4-ulopyranose 29
A 5.5 M t-BuOOH solution in nonane (870 µL, 4.78 mmol), DBU (434 µL, 2.90 mmol) and CH2Cl2
(13 mL) was added slowly to a stirred solution of 28 (1.32 g, 1.94 mmol) in CH2Cl2 (25 mL) cooled
to 0°C. After stirring at 20°C for 5 h, CH2Cl2 (70 mL), H2O (50 mL) and 0.5 M aq. Na2S2O3 (50 mL)
were added under vigorous stirring. After stirring at 20°C for 1 h, the aqueous layer was extracted with
CH2Cl2 (50 mL, three times). The combined org. extracts were washed with 1 M aq. HCl (50 mL),
then with brine (50 mL) and dried (MgSO4). Solvent evaporation afforded 1.40 g (100%) of 29, pure
enough for the next step. Flash chromatography on silica gel (3:1, light petroleum ether:EtOAc) gave a
white solid (82%): mp 47°C; [α]25589=+10.3, [α]25546=+4.5, [α]25435=+12.5, [α]25405=+21.0 (c 0.22,
CHCl3); UV (MeCN): λmax 216 (ε=10400); IR (KBr): ν 3420, 3030, 2870, 1730, 1495, 1455, 1360,
1120, 1095, 1065, 1030, 990, 735, 700 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.34–7.15 (m, 20H), 5.82
(s, H-1), 4.92–4.77 (m, 5H), 4.64 (d, 3J(H-10, H-20)=2.0 Hz, H-10), 4.57–4.49 (m, 5H), 3.79 (t, 3J(H-30,
H-40)=3J(H-30, H-20)=9.0 Hz, H-30), 3.77–3.74 (m, H2C(6)), 3.69 (t, 3J(H-40, H-50)=3J(H-40, H-30)=9.0
Hz, H-40), 3.68 (d, 3J(H-70, H-60)=2.8 Hz, H2C(70)), 3.57 (t, 3J(H-50, H-60)=3J(H-50, H-40)=9.0 Hz, H-
3
3
3
50), 3.57 (dd, J(H-2, H-1)=1.3 Hz, H-2), 3.44 (dd, J(H-20, H-30)=9.0, J(H-20, H-10)=2.0 Hz, H-20),
3.31 (dt, J(H-60, H-50)=9.0, J(H-60, H-70)=2.8 Hz, H-60); 13C NMR (100.6 MHz, CDCl3): δ 199.0
(s, C-4), 138.4, 138.2, 138.0, 137.95 (4s), 128.4–127.6 (20d), 98.1 (d, 1J(C, H)=178 Hz, C-1), 86.8 (d,
1J(C, H)=145 Hz, C-40), 79.4 (d, 1J(C, H)=140 Hz, C-60), 78.3 (d, 1J(C, H)=158 Hz, C-5), 77.7 (d, 1J(C,
H)=141 Hz, C-50), 77.2 (d, 1J(C, H)=143 Hz, C-30), 77.1 (d, 1J(C, H)=143 Hz, C-20), 75.5, 75.0, 74.9,
73.5 (4t, 1J(C, H)=142 Hz, CH2 (Bn)), 69.0 (t, 1J(C, H)=142 Hz, C-70), 65.4 (t, 1J(C, H)=155 Hz, C-6),
63.2 (d, 1J(C, H)=147 Hz, C-10), 59.5 (s, C-3), 50.5 (d, 1J(C, H)=188 Hz, C-2); CI-MS (NH3): m/z 712
(0.6, [M+18]+), 663 (2), 603 (1), 462 (0.5), 181 (2), 91 (100); anal. calcd for C41H42O10 (694.78): C,
70.88; H, 6.09; found: C, 70.83; H, 6.06.
3
3

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
277
5.15. 1,6:2,3-Dianhydro-3-C-[(1S)-2,6-anhydro-3,4,5,7-tetra-O-benzyl-D-glycero-D-gulo-heptitol-1-C-
yl]-β-D-gulo-pyranose 30
NaBH4 (0.12 g, 3.2 mmol) was added portionwise to a stirred solution of 29 (1.4 g, 2.0 mmol) in
MeOH (50 mL) cooled to 0°C. After stirring at 0°C for 1 h, CH2Cl2 (50 mL), H2O (50 mL) and 1
M aq. HCl (5 mL) were added. The aqueous layer was extracted with CH2Cl2 (50 mL, three times),
the combined org. extracts were washed with brine (50 mL) and dried (MgSO4). Solvent evaporation
and flash chromatography on silica gel (7:3, light petroleum ether:EtOAc) afforded 1.33 g (95%) of
white solid: mp 48°C; [α]25589=+8.7, [α]25546=+23, [α]25435=+30, [α]25405=+38 (c 0.09, CHCl3); UV
(MeCN): λmax 215 (ε=9100); IR (film): ν 3430, 3065, 2910, 1635, 1455, 1265, 1125, 1065, 735, 700
1
3
cm−1; H NMR (400 MHz, CDCl3): δ 7.34–7.20 (m, 20H), 5.52 (d, J(H-1, H-2)=0.9 Hz, H-1), 4.95-
4.41 (m, 8H), 4.59 (d, 3J(OH, H-4)=5.6 Hz, OH), 4.23 (dd, 3J(H-4, OH)=5.6, 3J(H-4, H-5)=4.9 Hz, H-4),
4.12 (dd, 2J=8.2, 3J(Hendo-6, H-5)=1.8 Hz, Hendo-6), 4.07 (ddd, 3J(H-5, Hexo-6)=6.1, 3J(H-5, H-4)=4.9,
3J(H-5, Hendo-6)=1.8 Hz, H-5), 3.78-3.75 (m, 4H, H-30, H-40, Hexo-6, OH), 3.69 (dd, 2J=9.7, 3J(Ha-70, H-
60)=2.9 Hz, Ha-70), 3.65 (ddd, 3J(H-60, H-50)=9.1, 3J(H-60, Hb-70)=6.9, 3J(H-60, Ha-70)=2.9 Hz, H-60),
3.56 (d, 3J(H-20, H-30)=8.2 Hz, H-20), 3.46 (dd, 2J(Hb-70, Ha-70)=9.7, 3J(Hb-70, H-60)=6.9 Hz, Hb-70),
3.43 (t, 3J(H-50, H-60)=3J(H-50, H-40)=9.1 Hz, H-50), 3.19 (d, 3J(H-10, OH)=7.6 Hz, H-10), 2.91 (br s,
H-2); 13C NMR (100.6 MHz, CDCl3): δ 138.3, 138.0, 137.6, 137.0 (4s), 128.4–127.4 (20d), 97.0 (d,
1J(C, H)=176 Hz, C-1), 86.7 (d, 1J(C, H)=142 Hz, C-40), 78.6 (d, 1J(C, H)=142 Hz, C-50), 78.3 (d, 1J(C,
H)=139 Hz, C-20), 77.4 (d, 1J(C, H)=144 Hz, C-30), 77.0 (d, 1J(C, H)=144 Hz, C-60), 75.6, 75.0, 74.95,
73.5 (4t, 1J(C, H)=143 Hz, CH2 (Bn)), 74.8 (d, 1J(C, H)=146 Hz, C-10), 72.5 (d, 1J(C, H)=159 Hz, C-5),
69.5 (t, 1J(C, H)=140 Hz, C-70), 67.0 (d, 1J(C, H)=152 Hz, C-4), 63.4 (t, 1J(C, H)=152 Hz, C-6), 57.0
(d, 1J(C, H)=180 Hz, C-2), 56.9 (s, C-3); CI-MS (NH3): m/z 714 (9, [M+18]+), 697 (2), 605 (2), 481 (3),
391 (3), 253 (6), 181 (13), 91 (100); anal. calcd for C41H44O10 (696.79): C, 70.67; H, 6.36; found: C,
70.66; H, 6.43.
5.16. 1,6:2,3-Dianhydro-3-C-[(1S)-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulo-pyranose
31
Metallic Na (1.2 g, 52 mmol) was added to liquid NH3 (30 mL, condensed at −78°C). A solution of
30 (1.32 g, 1.9 mmol) in anhydrous THF (10 mL) was added dropwise under stirring. After stirring at
−78°C for 40 min, solid NH4Cl (4 g) was added and the cooling bath removed. Once at 20°C, the residue
was taken in MeOH and purified by flash chromatography on silica gel (3:1, CH2Cl2:MeOH) affording
0.53 g (83%) of hygroscopic white solid: [α]25589=−11, [α]25546=−13, [α]25435=−23, [α]25405=−29
1
(c 0.36, MeOH); IR (KBr): ν 3415, 2925, 1640, 1415, 1125, 1085, 1015, 620 cm−1; H NMR (400
MHz, CD3OD): δ 5.56 (d, 3J(H-1, H-2)=1.1 Hz, H-1), 4.30 (ddd, 3J(H-5, Hexo-6)=6.1, 3J(H-5, H-4)=4.9,
3J(H-5, Hendo-6)=1.8 Hz, H-5), 4.24 (d, 3J(H-4, H-5)=4.9 Hz, H-4), 4.19 (br s, H-10), 4.06 (dd, 2J=8.0,
3J(Hendo-6, H-5)=1.8 Hz, Hendo-6), 3.87 (dd, 2J=11.9, 3J(Ha-70, H-60)=1.8 Hz, Ha-70), 3.78 (dd, 3J(H-20,
H-30)=9.1, 3J(H-20, H-10)=1.3 Hz, H-20), 3.72 (m, 2H, Hexo-6, Hb-70), 3.55 (t, 3J(H-30, H-40)=3J(H-30,
3
H-20)=9.1 Hz, H-30), 3.39 (t, J(H-40, H-50)=3J(H-40, H-30)=9.1 Hz, H-40), 3.33–3.30 (m, 2H, H-50,
1
H-60), 3.19 (br s, H-2); 13C NMR (100.6 MHz, CD3OD): δ 98.6 (d, J(C, H)=175 Hz, C-1), 81.4 (d,
1
1
1J(C, H)=142 Hz, C-60), 80.2 (d, J(C, H)=142 Hz, C-20), 79.6 (d, J(C, H)=140 Hz, C-40), 74.6 (d,
1J(C, H)=158 Hz, C-5), 71.0 (d, 1J(C, H)=145 Hz, C-50), 70.7 (d, 1J(C, H)=144 Hz, C-30), 68.2 (d, 1J(C,
H)=146 Hz, C-10), 67.4 (d, 1J(C, H)=148 Hz, C-4), 64.3 (t, 1J(C, H)=152 Hz, C-6), 62.5 (t, 1J(C, H)=143
Hz, C-70), 60.0 (s, C-3), 55.1 (d, 1J(C, H)=182 Hz, C-2); CI-MS (NH3): m/z 354 (1.2, [M+18]+), 247 (1),
126 (94), 95 (100), 83 (81).

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Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
5.17. 4-O-Acetyl-1,6:2,3-dianhydro-3-C-[(1S)-1,3,4,5,7-penta-O-acetyl-2,6-anhydro-D-glycero-D-
gulo-heptitol-1-C-yl]-β-D-gulo-pyranose 32
A mixture of 31 (530 mg, 1.57 mmol), Ac2O (6 mL), pyridine (10 mL) and 4-dimethylaminopyridine
(0.5 mg) was stirred at 20°C for 15 h. Solvent evaporation in vacuo gave a residue that was taken in
toluene (10 mL) and the solvent was evaporated to dryness in vacuo. The latter operation was repeated and
the residue purified by flash chromatography on silica gel (1:2, light petroleum ether:EtOAc) affording
878 mg (95%) of white solid: mp 66°C; [α]25589=+12, [α]25546=+13, [α]25435=+22, [α]25405=+25 (c
0.38, CHCl3); IR (KBr): ν 1755, 1435, 1375, 1230, 1120, 1035, 910 cm−1; 1H NMR (400 MHz, CDCl3):
δ 5.59 (s, H-1), 5.34 (d, 3J(H-4, H-5)=4.8 Hz, H-4), 5.22 (t, 3J(H-40, H-50)=3J(H-40, H-30)=9.7 Hz, H-
3
3
40), 5.10 (t, J(H-30, H-40)=3J(H-30, H-20)=9.7 Hz, H-30), 5.07 (t, J(H-50, H-60)=3J(H-50, H-40)=9.7
Hz, H-50), 4.86 (br s, H-10), 4.48 (ddd, 3J(H-5, Hexo-6)=5.9, 3J(H-5, H-4)=4.8, 3J(H-5, Hendo-6)=1.9 Hz,
H-5), 4.33 (dd, 2J=12.4, 3J(Ha-70, H-60)=4.9 Hz, Ha-70), 4.13 (dd, 2J=12.4, 3J(Hb-70, H-60)=2.0 Hz, Hb-
70), 4.02 (dd, 3J(H-20, H-30)=9.7, 3J(H-20, H-10)=1.9 Hz, H-20), 3.84 (dd, 2J=8.1, 3J(Hendo-6, H-5)=1.9
Hz, Hendo-6), 3.80 (dd, 2J=8.1, 3J(Hexo-6, H-5)=5.9 Hz, Hexo-6), 3.75 (ddd, 3J(H-60, H-50)=9.7, 3J(H-60,
Ha-70)=4.9, 3J(H-60, Hb-70)=2.0 Hz, H-60), 3.18 (s, H-2), 2.15, 2.11, 2.08, 2.04, 2.00, 1.99 (6s, 6 AcO).
13C NMR (100.6 MHz, CDCl3): δ 170.5, 170.1, 169.5, 169.3, 169.0, 168.5 (6s), 96.9 (d, 1J(C, H)=177
Hz, C-1), 76.6, 76.4 (2d, 1J(C, H)=144, 1J(C, H)=133 Hz, C-20, C-60), 74.1 (d, 1J(C, H)=152 Hz, C-40),
1
1
1
1
70.1 (d, J(C, H)=160 Hz, C-5), 68.1, 67.6, 67.4 (3d, J(C, H)=156, J(C, H)=157, J(C, H)=155 Hz,
C-4, C-30, C-50), 66.4 (d, 1J(C, H)=148 Hz, C-10), 63.5 (t, 1J(C, H)=156 Hz, C-6), 62.0 (t, 1J(C, H)=149
Hz, C-70), 53.9 (s, C-3), 52.6 (d, J(C, H)=184 Hz, C-2), 20.7, 20.6, 20.4, 20.35, 20.3, 20.1 (6q, J(C,
H)=130 Hz, 6 Ac); CI-MS (NH3): m/z 606 (15, [M+18]+), 529 (2), 117 (5), 83 (100); anal. calcd for
C25H32O16 (588.52): C, 51.02; H, 5.48; found: C, 50.84; H, 5.30.
1
1
5.18. 1,4,6-Tri-O-acetyl-2,3-anhydro-3-C-[(1S)-1,3,4,5,7-penta-O-acetyl-2,6-anhydro-D-glycero-D-
gulo-heptitol-1-C-yl]-α-D-gulo-pyranose 33 and 4,6-di-O-acetyl-2,3-anhydro-3-C-[(1S)-1,3,4,5,7-
penta-O-acetyl-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulo-pyranose 34
A mixture of 32 (225 mg, 0.38 mmol), Ac2O (1.35 mL) and CF3COOH (1 mL) was stirred at 20°C
for 25 h. This was poured into ice (10 mL) and neutralized with sat. aq. solution of NaHCO3 (pH 8). The
mixture was extracted with EtOAc (10 mL, three times). The combined organic extracts were washed
with brine (30 mL) and dried (MgSO4). Solvent evaporation and flash chromatography on silica gel (1:1,
light petroleum ether:EtOAc) afforded 93 mg (37%) of pyranose 33, 100 mg (38%) of pyranose 34 and
43 mg (16%) of 32.
Data for 33: white solid, mp 81°C; [α]25589=+16, [α]25546=+21, [α]25435=+32, [α]25405=+40 (c 0.22,
1
CHCl3); IR (KBr): ν 1750, 1435, 1375, 1230, 1165, 1100, 1035, 600 cm−1; H NMR (400 MHz,
3
3
3
CDCl3): δ 6.34 (d, J(H-1, H-2)=2.9 Hz, H-1), 5.65 (d, J(H-4, H-5)=1.1 Hz, H-4), 5.16 (dd, J(H-40,
H-50)=9.5, J(H-40, H-30)=9.5 Hz, H-40), 5.08 (dd, J(H-30, H-40)=9.5, J(H-30, H-20)=9.5 Hz, H-30),
3
3
3
4.99 (dd, 3J(H-50, H-60)=9.5, 3J(H-50, H-40)=9.5 Hz, H-50), 4.89 (d, 3J(H-10, H-20)=2.0 Hz, H-10), 4.30
(ddd, J(H-5, Ha-6)=7.1, J(H-5, Hb-6)=4.4, J(H-5, H-4)=1.1 Hz, H-5), 4.26 (dd, J=12.3, J(Ha-70,
3
3
3
2
3
H-60)=2.0 Hz, Ha-70), 4.09 (dd, J=12.3, J(Hb-70, H-60)=7.8 Hz, Hb-70), 4.07 (dd, J=11.6, J(Hb-6,
2
3
2
3
2
3
3
H-5)=4.4 Hz, Hb-6), 3.88 (dd, J=11.6, J(Ha-6, H-5)=7.1 Hz, Ha-6), 3.74 (d, J(H-2, H-1)=2.9 Hz,
H-2), 3.70 (dd, 3J(H-20, H-30)=9.5, 3J(H-20, H-10)=2.0 Hz, H-20), 3.68 (ddd, 3J(H-60, H-50)=9.5, 3J(H-
60, Hb-70)=7.8, 3J(H-60, Ha-70)=2.0 Hz, H-60), 2.17, 2.14, 2.13, 2.10, 2.05, 2.03, 2.00, 2.00 (8s, 24H, 8
AcO); 13C NMR (100.6 MHz, CDCl3): δ 170.2–169.3 (8s), 87.5 (d, J(C, H)=172 Hz, C-1), 76.6 (2d,
1
1J(C, H)=144, J(C, H)=144 Hz, C-20, C-60), 74.0 (d, J(C, H)=154 Hz, C-40), 68.4 (d, J(C, H)=151
1
1
1

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
279
Hz, C-50), 68.1 (d, 1J(C, H)=148 Hz, C-5), 67.3 (d, 1J(C, H)=155 Hz, C-30), 67.1 (d, 1J(C, H)=147 Hz,
C-10), 66.4 (d, 1J(C, H)=151 Hz, C-4), 62.6 (t, 1J(C, H)=149 Hz, C-70), 61.6 (t, 1J(C, H)=152 Hz, C-6),
1
1
55.7 (s, C-3), 55.1 (d, J(C, H)=188 Hz, C-2), 20.9–20.4 (8q, J(C, H)=130 Hz, 8 Ac); CI-MS (NH3):
m/z 708 (89, [M+18]+), 663 (3), 631 (54), 606 (27), 83 (100); anal. calcd for C29H38O19 (690.61): C,
50.44; H, 5.55; found: C, 50.48; H, 5.59.
Data for 34: white solid, mp 68°C; [α]25589=+35, [α]25546=+45, [α]25435=+50, [α]25405=+55 (c 0.02,
CHCl3); UV (MeCN): final absorbance: 191 (ε=3200); IR (KBr): ν 3475, 1750, 1375, 1235, 1040,
905, 600 cm−1; H NMR (400 MHz, CDCl3): δ 5.61 (br s, H-4), 5.42 (br s, H-1), 5.16 (t, J(H-40, H-
50)=3J(H-40, H-30)=9.5 Hz, H-40), 5.08 (t, 3J(H-30, H-40)=3J(H-30, H-20)=9.5 Hz, H-30), 5.02 (t, 3J(H-50,
H-60)=3J(H-50, H-40)=9.5 Hz, H-50), 4.86 (d, 3J(H-10, H-20)=1.7 Hz, H-10), 4.25–4.21 (m, 2H, H-5, Ha-
70), 4.14–4.09 (m, 2H, Ha-6, Hb-70), 3.87 (dd, 2J=11.5, 3J(Hb-6, H-5)=7.1 Hz, Hb-6), 3.73–3.64 (m, 3H,
H-20, H-2, H-60), 3.26 (br s, OH), 2.16, 2.11, 2.10, 2.05, 1.99 (7s, 21H, 7 AcO); 13C NMR (100.6 MHz,
CDCl3): δ 170.6, 170.5, 170.2, 169.8, 169.5, 169.4, 169.3 (7s), 87.3 (d, 1J(C, H)=169 Hz, C-1), 76.6 (d,
1J(C, H)=146 Hz, C-20, C-60), 74.1 (d, 1J(C, H)=152 Hz, C-40), 68.4 (d, 1J(C, H)=154 Hz, C-50), 67.6
(d, 1J(C, H)=147 Hz, C-10), 67.4 (d, 1J(C, H)=149 Hz, C-30), 66.5 (d, 1J(C, H)=151 Hz, C-4), 66.0 (d,
1J(C, H)=148 Hz, C-5), 62.4 (t, 1J(C, H)=149 Hz, C-70), 62.2 (t, 1J(C, H)=149 Hz, C-6), 57.5 (d, 1J(C,
1
3
1
H)=185 Hz, C-2), 57.3 (s, C-3), 20.8-20.3 (7q, J(C, H)=130 Hz, 7 Ac); CI-MS (NH3): m/z 666 (100,
[M+18]+), 631 (29), 228 (10), 169 (7), 97 (13).
5.19. 2,3-Anhydro-3-C-[(1S)-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulo-pyranose 5
A mixture of 33 (73 mg, 0.11 mmol) and sat. solution of NH3 in MeOH (5 mL) was stirred at 20°C
1
for 6 h. Solvent evaporation in vacuo afforded pure 5 and acetamide (by H NMR). Chromatography
on silica gel (2:1, CHCl3:MeOH) afforded 16 mg (45%) of pure 5 (a single anomer): hygroscopic white
solid, [α]25589=+4.8, [α]25546=+6.4, [α]25435=+12.2, [α]25405=+14.6 (c 0.31, MeOH); UV (MeCN): final
absorbance: 194 (ε=3000); IR (KBr): ν 3390, 2925, 1640, 1415, 1090, 1040, 570 cm−1; 1H NMR (600
3
3
MHz, 323 K, CD3OD): δ 5.25 (s, H-1), 4.53 (d, J(H-10, H-20)=2.0 Hz, H-10), 4.26 (d, J(H-4, H-
3
3
3
5)=3.6 Hz, H-4), 3.96 (ddd, J(H-5, Hb-6)=6.9, J(H-5, Ha-6)=4.4, J(H-5, H-4)=3.6 Hz, H-5), 3.87
(dd, 2J=11.9, 3J(Ha-70, H-60)=2.1 Hz, Ha-70), 3.74 (dd, 2J=11.4, 3J(Ha-6, H-5)=4.4 Hz, Ha-6), 3.71 (t,
3J(H-30, H-40)=3J(H-30, H-20)=9.2 Hz, H-30), 3.65 (d, J(H-2, H-1)=0.5 Hz, H-2), 3.62 (dd, J=11.4,
3J(Hb-6, H-5)=6.9 Hz, Hb-6), 3.60 (dd, 2J=11.9, 3J(Hb-70, H-60)=7.8 Hz, Hb-70), 3.58 (dd, 3J(H-20, H-
30)=9.2, 3J(H-20, H-10)=2.0 Hz, H-20), 3.44 (t, 3J(H-40, H-50)=3J(H-40, H-30)=9.2 Hz, H-40), 3.32 (ddd,
3J(H-60, H-50)=9.2, 3J(H-60, Hb-70)=7.8, 3J(H-60, Ha-70)=2.1 Hz, H-60), 3.18 (t, 3J(H-50, H-60)=3J(H-50,
H-40)=9.2 Hz, H-50). 13C NMR (100.6 MHz, CD3OD): δ 95.8 (d, 1J(C, H)=172 Hz, C-1), 82.4 (d, 1J(C,
H)=142 Hz, C-60), 79.9, 79.8 (2d, 1J(C, H)=140 Hz, C-20, C-40), 75.9 (d, 1J(C, H)=146 Hz, C-4), 72.7
(d, 1J(C, H)=144 Hz, C-5), 72.1 (d, 1J(C, H)=143 Hz, C-50), 70.7 (d, 1J(C, H)=146 Hz, C-30), 68.1 (s,
C-3), 65.4 (d, 1J(C, H)=145 Hz, C-10), 64.2 (t, 1J(C, H)=143 Hz, C-6), 63.8 (t, 1J(C, H)=144 Hz, C-70),
60.3 (d, 1J(C, H)=193 Hz, C-2). CI-MS (NH3): m/z 372 (13, [M+18]+), 354 (6), 282 (16), 252 (17), 210
(37), 192 (100), 127 (69), 92 (64). Electrospray-MS (+, 50:50:1, MeCN:H2O:AcOH) m/z 396.1 (100,
[M+MeCN +1]+), 355.2 (20, [M+1]+); anal. calcd: see 33.
3
2
5.20. 1,6:2,3-Dianhydro-3-C-[(1S)-2,6-anhydro-3,4,5,7-tetra-O-benzyl-D-glycero-D-gulo-heptitol-1-C-
yl]-β-D-gulo-pyranose-10,4-acetonide 35
A mixture of 30 (223 mg, 0.32 mmol), 2,2-dimethoxypropane (6 mL), dry acetone (6 mL) and pTsOH
(60 mg) was stirred at 20°C for 15 h. After the addition of EtOAc (10 mL) and H2O (20 mL), the aq.

280
Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
phase was extracted with EtOAc (10 mL, three times). The combined org. extracts were washed with a
sat. aq. solution of NaHCO3 (20 mL), brine (20 mL) and dried (MgSO4). Solvent evaporation and flash
chromatography on silica gel (4:1, light petroleum ether:EtOAc) afforded 193 mg (82%) of white solid:
mp 38°C; [α]25589=+18, [α]25546=+21, [α]25435=+34, [α]25405=+42 (c 0.2, CHCl3); UV (MeCN): λmax
217 (ε=16600); IR (KBr): ν 3520, 3030, 2905, 2865, 1495, 1455, 1365, 1225, 1120, 1085, 1030, 925,
735, 700 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.41–7.15 (m, 20H), 5.54 (d, 3J(H-1, H-2)=1.0 Hz, H-1),
3
3
3
4.97–4.61 (m, 8H), 4.47 (d, J(H-10, H-20)=1.4 Hz, H-10), 4.44 (ddd, J(H-5, Hexo-6)=6.2, J(H-5, H-
4)=5.4, 3J(H-5, Hendo-6)=1.7 Hz, H-5), 4.35 (d, 3J(H-4, H-5)=5.4 Hz, H-4), 4.24 (dd, 2J=8.2, 3J(Hendo-6,
H-5)=1.7 Hz, Hendo-6), 3.83 (t, 3J(H-30, H-40)=3J(H-30, H-20)=9.3 Hz, H-30), 3.77 (dd, 2J=8.2, 3J(Hexo
-
6, H-5)=6.2 Hz, Hexo-6), 3.75 (d, J(H-70, H-60)=2.7 Hz, H2C(70)), 3.65 (2t, J(H-40, H-50)=3J(H-40,
3
3
H-30)=3J(H-50, H-60)=3J(H-50, H-40)=9.3 Hz, H-40, H-50), 3.35 (br d, J(H-60, H-50)=9.3 Hz, H-60),
3
3.09 (br d, 3J(H-20, H-30)=9.3 Hz, H-20), 2.97 (br s, H-2), 1.44, 1.35 (2s, 2 Me); 13C NMR (100.6 MHz,
CDCl3): δ 138.6, 138.4, 138.3, 138.1 (4s), 128.4–127.4 (20d), 101.6 (s), 97.6 (d, 1J(C, H)=175 Hz, C-1),
87.5 (d, J(C, H)=140 Hz, C-40), 79.5 (d, J(C, H)=146 Hz, C-60), 78.2 (d, J(C, H)=146 Hz, C-50),
1
1
1
77.6 (d, J(C, H)=151 Hz, C-30), 75.4, 74.9, 74.85, 73.3 (4t, J(C, H)=143 Hz, 4 CH2 (Bn)), 75.3 (d,
1J(C, H)=139 Hz, C-20), 71.6 (d, 1J(C, H)=158 Hz, C-5), 68.3 (t, 1J(C, H)=142 Hz, C-70), 65.3 (d, 1J(C,
H)=142 Hz, C-10), 63.7 (d, 1J(C, H)=151 Hz, C-4), 63.4 (t, 1J(C, H)=152 Hz, C-6), 58.7 (s, C-3), 49.9 (d,
1J(C, H)=181 Hz, C-2), 24.6, 24.2 (2q, 1J(C, H)=126 Hz, 2 Me); CI-MS (NH3): m/z 754 (95, [M+18]+),
645 (4), 181 (9), 124 (21), 108 (62), 91 (100).
1
1
5.21. 1,6:2,3-Dianhydro-3-C-[(1S)-2,6-anhydro-D-glycero-D-gulo-heptitol-1-C-yl]-β-D-gulo-
pyranose-10,4-acetonide 36
Metallic Na (170 mg, 7.4 mmol) was added to liquid NH3 (5 mL, condensed at −78°C). A solution of
35 (193 mg, 0.26 mmol) in anhydrous THF (1.4 mL) was added dropwise under stirring. After stirring
at −78°C for 20 min, solid NH4Cl (0.6 g) was added and the cooling bath removed. Once at 20°C, the
residue was taken in MeOH and purified by flash chromatography on silica gel (5:1, CH2Cl2:MeOH)
affording 74 mg (75%) of white solid: mp 135–138°C; [α]25589=−22, [α]25546=−32, [α]25435=−52,
[α]25405=−67 (c 0.11, MeOH); UV (MeCN): final absorbance: 194 (ε=900); IR (KBr): ν 3385, 2920,
1
1655, 1385, 1225, 1125, 1080, 1030, 925, 875, 610, 510 cm−1; H NMR (400 MHz, CD3OD): δ 5.57
(d, 3J(H-1, H-2)=1.0 Hz, H-1), 4.61 (s, H-10), 4.47 (ddd, 3J(H-5, Hexo-6)=6.2, 3J(H-5, H-4)=5.4, 3J(H-5,
Hendo-6)=1.8 Hz, H-5), 4.29 (d, 3J(H-4, H-5)=5.4 Hz, H-4), 4.23 (dd, 2J=8.2, 3J(Hendo-6, H-5)=1.8 Hz,
Hendo-6), 3.81 (dd, 2J=12.1, 3J(Ha-70, H-60)=2.4 Hz, Ha-70), 3.76 (dd, 2J=8.2, 3J(Hexo-6, H-5)=6.2 Hz,
2
3
Hexo-6), 3.65 (dd, J=12.1, J(Hb-70, H-60)=5.1 Hz, Hb-70), 3.37–3.28 (m, 3H, H-30, H-40, H-50), 3.13
(ddd, 3J(H-60, H-50)=9.4, 3J(H-60, Hb-70)=5.1, 3J(H-60, Ha-70)=2.4 Hz, H-60), 2.99 (br s, H-2), 2.95 (dd,
3J(H-20, H-30)=9.4, 3J(H-20, H-10)=0.7 Hz, H-20), 1.51 (s, Meb), 1.42 (s, Mea); 13C NMR (100.6 MHz,
CD3OD): δ 103.4 (s), 98.9 (d, 1J(C, H)=176 Hz, C-1), 82.2 (d, 1J(C, H)=138 Hz, C-60), 80.3, 71.2, 70.5
(3d, 1J(C, H)=143, 1J(C, H)=143, 1J(C, H)=146 Hz, C-30, C-40, C-50), 76.1 (d, 1J(C, H)=140 Hz, C-20),
72.9 (d, 1J(C, H)=160 Hz, C-5), 66.3 (d, 1J(C, H)=142 Hz, C-10), 65.4 (d, 1J(C, H)=151 Hz, C-4), 64.2
1
1
1
(t, J(C, H)=153 Hz, C-6), 62.7 (t, J(C, H)=143 Hz, C-70), 60.3 (s, C-3), 50.6 (d, J(C, H)=181 Hz,
C-2), 24.6, 24.2 (2q, J(C, H)=127 Hz, 2 Me); CI-MS (NH3): m/z 395 (3, [M+18]+), 338 (5), 302 (4),
1
213 (17), 191 (7), 155 (12), 109 (100).

Y.-H. Zhu et al. / Tetrahedron: Asymmetry 11 (2000) 263–282
281
Acknowledgements
This work was supported by the Swiss National Science Foundation (Grant No. 20-55567.98). We also
thank the European COST program (action COST D13/0001/99) for their encouragement.
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