Stereoselective Glycosylation of D-Galactals by Diethyl
Phosphorochloridite- and AlCl3-assisted Ferrier
Rearrangement
Yen-Bo Chen,1,2 Su-I Wang,2 Zi-Ping Lin,2 Chun-Hung Lin,3 Min-Tsang Hsieh,1,4 and
Hui-Chang Lin1,2,*
1
School of Pharmacy, China Medical University,
No. 91, Hsueh-Shih Rd., Taichung, 40402, Taiwan
2
Graduate Institute of Pharmaceutical Chemistry, China Medical University,
No. 91, Hsueh-Shih Rd., Taichung, 40402, Taiwan
3
Institute of Biological Chemistry, Academia Sinica,
No. 128, Academia Road, Section 2, Nan-Kang, Taipei, 11529, Taiwan
4
Chinese Medicinal Research and Development Center, China Medical University
hospital, No. 2, Yude Rd., Taichung, 40447, Taiwan
*Corresponding Author: Dr. Hui-Chang Lin (Tel: +886-4-22053366, ext-5612, Fax:
+886-4-22078083, E-mail: lhc550005@yahoo.com.tw, huichang@mail.cmu.edu.tw).
Key words: 2,3-unsaturated glycopyranosides, Ferrier rearrangement, diethyl
phosphorochloridite, glycal, Lewis acid
Abstract
-2,3-Unsaturated galactosides were synthesized in good to excellent yields by the
initial activation of D-galactals with diethyl phosphorochloridite and the subsequent
glycosyl addition via Ferrier rearrangement with various O-nucleophiles in the
presence of AlCl3. The two-step reactions were carried out in one-pot and finished
within 60 min in 81-95% yield to give the glycoside products with excellent
-stereoselectivity.
1
2
Introduction
2,3-Unsaturated-O-glycosides are useful building blocks for the synthesis of
various bioactive compounds, such as nucleosides,1 antibiotics,2 glycopeptides,3
oligosaccharides,4 uronic acids,5 and other natural products.6 The double bond in C2
and C3 of the pyranose ring can be further transformed via several types of reactions
(e.g. dihydroxylation,8 hydrogenation,9 epoxidation,10 and aminohydroxylation11) to
generate structural complexity and diversity. Preparation of 2,3-unsaturated
glycosides via Ferrier rearrangement has drawn attention in the past several decades.
This rearrangement is believed to involve a cyclic allylic oxocarbonium intermediate
that is formed via displacement of the C-3 substituent in an endo-glycal, followed by
the attack of a nucleophile to the anomeric carbon preferentially from the
quasi-equatorial orientation.7 A wide range of catalysts have been employed to
facilitate the syntheses, such as BF3.OEt2,12 FeCl3,13 InCl3,14 Montmorillonite K-10,15
SnCl4,16 K5Co-W12O40,17 BiCl3,18 Dy(OTf)3,19 CeCl3.7H2O,20 ZnCl2,21 Sc(OTf)3,22
IDCP,23 TMSOTf,24 NIS,25 LiBF4,26 trichloroacetimidate,27 Fe(NO3)3.9H2O,28 InBr3,29
ZrCl4,30
I2,31
DMF-DMA,37
CAN,32
HClO4-SiO2,33
Pd(PhCN)2Cl2,38
DDQ,34
Fe(OTf)3,39
Bi(NO3)3.5H2O,35
Er(OTf)3,40
NbCl5,36
ZnCl2/Al2O3,41
(S)-Camphorsulfonic acid,42 H3PO4,43 TfOH-SiO2,44 NaHSO4-SiO2,45 and t-BuOK.46
Successful Ferrier rearrangement can be carried out when endo-glycals
possessing a good leaving group at C-3 position, including trichloroacetamidate,47
tert-butyloxycarbonyl ester,48 n-pentenoyl ester,49 benzoyl ester,50 carbonate,51
propargyl ether,52 and benzyl ether.53 To the best of our knowledge, there is no report
to derive from 3-O-diethoxyphosphanyl-D-galactal. However, the diethoxyphosphanyl
group can be easily activated in the presence of acid or Lewis acid.55 Herein we
developed
an
efficient
two-step,
one-pot
synthesis
to
prepare
2,3-unsaturated-O-glycosides. 3-Hydroxy-D-galactal was reacted with diethyl
3
phosphorochloridite
and
triethylamine
to
give
in
situ
the
intermediate
3-O-diethoxyphosphanyl-D-galactal, followed by rearrangement and glycosyl addition
with
various
O-nucleophiles
in
the
presence
of
AlCl3
to
give
2,3-unsaturated-O-glycosides
Result and Discussion
4,6-Di-O-benzyl-3-hydroxy-D-galactal 1a, prepared from 3,4,6-tri-O-acetyl-Dgalactal
according
to
previous
procedure,54
was
reacted
with
diethyl
phosphorochloridite in the presence of Lewis bases (3.0 equiv) to produce the
3-O-diethoxyphosphanyl-D-galactal as the intermediate, and was then followed by
C1-addition of n-hexanol to give the glycosyl adduct. Five different Lewis bases (3.0
equiv) were examined, including triethylamine (Et3N), 4-dimethylaminopyridine
(DMAP), 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), potassium carbonate (K2CO3),
and potassium tert-butoxide (t-BuOK), as shown in entries i-v of Table 1. The
reactions were all carried out in dichloromethane at 0 oC for 1 h. Among these
reactions, Et3N was found to provide the desired 2,3-unsaturated-O-glycoside (4) with
the highest isolated yield (91%) and moderate stereoselectivity (ratio of /β-anomers:
78/22).
Meanwhile, we investigated the solvent effect by examining the reactions in THF,
MeCN, DMF, CH2Cl2 and toluene (entries vi-ix of Table 1). The reactions in toluene
and dicholomethane were found to afford higher yields and stereoselectivity than
those in other solvents. Among the reactions, the combined use of CH2Cl2 and Et3N
gave the desired product (4) in the highest isolated yield (91%) with moderate
stereoselectivity (ratio of –anomers: 78/22) (see entry i in Table 1). Interestingly,
3-O-diethoxyphosphanyl-D-galactal (3a) appeared to be more active than glycosyl
4
diethyl phosphites (the phosphite is attached to the anomeric center)55 because of
different stability (3a could not be isolated but the latter could be purified and
characterized).
In order to improve the resulting α-stereoselectivity, addition of Lewis acid was
considered in the Ferrier rearrangement-mediated glycosylation. We generated
4,6-di-O-benzyl-3-diethyl phosphite-D-galactal (3a) in situ, followed by the addition
of n-hexanol and Lewis acid. A CH2Cl2 solution of 4,6-di-O-benzyl-3-diethyl
phosphite-D-galactal 3a and n-hexanol was treated with 1.0 equiv of various Lewis
acids at 0 oC for 30 min, including zinc chloride (ZnCl2), calcium chloride (CaCl2),
mercury(II) sulfate (HgSO4), iron chloride (FeCl3), aluminum chloride (AlCl3), and
5
tin(IV) chloride (SnCl4). The use of AlCl3 was concluded to provide the highest
isolated yield (94%) and stereoselectivity (ratio of –anomers: 92/8) (entry v in
Table 2).
To our delight, high yields and stereoselectivity were also obtained when the
same condition was applied to the reactions with other alcohol nucleophiles (entries
i-vi in Table 3), as well as those with a similar substrate (1b) (entries vii-ix).
6
Furthermore, various sugar nucleophiles were examined. Their reactions gave the
desirable 2,3-unsaturated glycoside products 17–22 in 81–86% yields with excellent
-stereoselectivity (Table 4). It is realized that the nucleophile preferentially attacks
from the bottom face of the sugar ring, which is not only consistent with the anomeric
effect, but also favorable by the less steric hindrance resulting from the
C4-substitutent. All the product structures, including the new stereogenic
configurations, were rigorously determined by using the COSY and NOSY methods,
in agreement with previous reports.56 For example, the 1H NMR spectrum of
compound 17 showed the characteristic signals of H1 ( 5.43, d), H2 ( 5.90, dd), and
7
H3 ( 6.02, dd). In the corresponding 13C NMR spectrum, the resonances at  96.30,
129.43, and 126.97 were assigned to C1, C2 and C3 of 17, respectively.
We previously applied microwave- and AlCl3-assisted glycosylation of
C3-substituted endo-galactals (that contains a benzyloxy, acetate or hydroxy group at
8
C3) where these reactions were found to proceed via protonation to produce
-2-deoxyglycosides.48b Those results are different from what we observed here (e.g.
formation of 2,3-unsaturated O-glycosides), indicating that the substituent at C3 plays
a role in affecting the reactivity and needs to be labile enough to promote Ferrier
rearrangement.
In addition, exo-glycal 2 was subjected to the similar 2-step procedure. The
glycosidations were successful with various alcohols, including methanol, n-butanol,
n-hexanol, allyl alcohol, benzyl alcohol, isopropanol, and cyclohexanol. The resulting
glycoside products 23–2953c were obtained in 74–86% yields with exclusive
-stereoselectivity (Table 5).
9
We proposed a plausible mechanism to interpret the observed rearrangement and
stereoselectivity. As shown in Scheme 1, the first step reaction was expected to result
in the formation of 3-O-diethoxyphosphanyl-D-galactal (3a). The subsequent addition
of AlCl3 not only led to the possible chelation of C3-, C4- and C6-substituents with
the Lewis acid, but also facilitated the rearrangement to form the conjugated
oxocarbenium ion intermediate 31. At this stage, the blockade of the sugar top face
(caused by the chelation) is critical to dominate the nucleophilic attack from the
bottom face, which explains the -stereoselectivity. The final product (4) was
obtained by the addition of hexanol (serving as the nucleophile) to the oxocarbenium
intermediate.
Scheme 1
In conclusion, -2,3-unsaturated glycopyranosides were successfully prepared
10
by glycosyl addition of endo-galactals with several O-nucleophiles, including simple
alcohols and sugar derivatives. The two-step synthesis was operated in one pot via
tandem phosphanylation and Ferrier rearrangement-mediated glycosylation. This
developed method was also applicable to the addition of exo-glycals.
Acknowledgment
The
authors
thank
the
National
Science
Council
of
Taiwan
(MOST
103-2113-M-039-004) and China Medical University, Taiwan (CMU95-194) for their
financial support.
Experimental Section
General Procedure: All purchased chemicals were of reagent grade. All reactions
were carried out under a nitrogen atmosphere and monitored by TLC analysis (layer
thickness: 250 m). Column chromatography was carried out with silica gel 60 (70–
230 mesh for gravity column, or 230–400 mesh for flash column). Commercially
available reagents were directly used without further purification unless otherwise
noted. Dichloromethane, ethyl acetate, hexanes, and methanol were purchased from
Mallinckrodt Chemical Co. The following compounds were purchased from Acros
Chemical Co, including methanol, benzyl alcohol, n-hexanol, cyclohexanol,
isopropanol, allyl alcohol, iodomethane, tri-O-acetyl-D-galactal, benzyl chloride,
potassium carbonate, sodium hydride, diethyl chlorophosphite, triethylamine,
1,8-diazabicyclo[5.4.0]undec-7-ene,
4-dimethylaminopyridine,
potassium
tert-butoxide, aluminum chloride, iron chloride, tin(IV) chloride, calcium chloride,
zinc chloride, mercury(II) sulfate, 1,2:3,4-di-O-isopropylidene--D-galactopyranose.
Proton NMR spectra were recorded at a Bruker spectrometer (200 or 400 MHz) with
CDCl3 (H 7.24) and DMSO-d6 (H 2.50) as the internal standard; Carbon-13 NMR
spectra were recorded at 50 or 100 MHz with CDCl3 [C 77.0 (central line of a
11
triplet)]. Splitting patterns are shown by the abbreviations, such as s (singlet), d
(doublet), t (triplet), q (quartet), and m (multiplet).
Typical
Procedure
of
Glycosylation
for
Preparing
2,3-Unsaturated
Glycopyranoside Derivatives 4-12, 33. To a solution of endo-galactal 1 (1.0 equiv.)
in anhydrous CH2Cl2 (1.5 mL) was added diethyl phosphorochloridite (1.2 equiv.) and
Et3N (3.0 equiv.). The reaction mixture was stirred at 0 C under N2 for 30 min. After
the phosphanylation was completed, one equivalent of AlCl3 and three equivalents of
an alcohol substrate were added into the reaction mixture and stirred at 0 C for 30
min. Once the reaction was completed, the resulting solution was added to CH2Cl2 (50
mL), washed with H2O (20 mL × 2), and brine (20 mL × 2). The organic layer was
collected, concentrated under reduced pressure and purified by silica gel column
chromatography with 33% EtOAc in hexanes to give the desired product
(2,3-unsaturated glycopyranosides 4–12 and 33) in 85–94 % yields.
Hexyl 4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 4: Pale yellow oil;
IR (CHCl3) 2966, 1585, 1398, 1099 cm-1; 1H NMR (CDCl3, 400 MHz)  7.30-7.21
(10H, m, ArH), 6.07 (1H, dd, J3,4 = 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.95 (1H, dd, J2,1 =
3.2 Hz, J2,3 = 10.0 Hz, H2), 5.01 (1H, d, J1,2 = 3.2 Hz, H1), 4.61-4.50 (4H, m, CH2Ph),
4.26-4.22 (1H, m, H5), 3.81-3.68 (4H, m, H4, H6a, H6b, H1b’), 3.46-3.41 (1H, m,
H1a’), 1.57-1.53 (2H, m, H2’), 1.31-1.22 (6H, m, H3’, H4’, H5’), 0.83 (3H, t, J = 6.8
Hz, H6’);
13
C NMR (CDCl3, 100 MHz)  138.36, 129.80, 128.32, 128.31,
128.30, 128.29, 127.74, 127.73, 127.60, 127.54, 127.53, 127.52, 126.87, 90.05, 73.39,
70.98, 69.59, 69.45, 68.36, 67.37, 31.61, 29.72, 25.86, 22.58, 14.01; FAB-MS m/z (rel
intens) 411 (M + H+, 1), 253 (6), 181 (22), 105 (22), 91 (100), 57 (73); HRMS (FAB)
m/z calcd for C26H35O4 (M + H+) 411.2530, found 411.2538. Anal. Calcd for
C26H34O4; C: 76.06; H: 8.35. Found: C: 76.10; H: 8.37.
Methyl 4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 5: Pale yellow
12
oil; IR (CHCl3) 2945, 1585, 1398, 1099 cm-1; 1H NMR (CDCl3, 400 MHz) 
7.27-7.17 (10H, m, ArH), 6.03 (1H, dd, J3,4 = 5.0 Hz, J3,2 = 10.0 Hz, H3), 5.91 (1H,
dd, J2,1 = 2.5 Hz, J2,3 = 10.0 Hz, H2), 4.88 (1H, d, J1,2 = 2.5 Hz, H1), 4.56 (1H, d, J =
12.0 Hz, CH2Ph), 4.55 (1H, d, J = 12.0 Hz, CH2Ph), 4.50 (1H, d, J = 12.0 Hz,
CH2Ph), 4.47 (1H, d, J = 12.0 Hz, CH2Ph), 4.17-4.16 (1H, m, H5), 3.75 (1H, dd, J6a,5
= 6.5 Hz, J6a,6b = 10.0 Hz, H6a), 3.69 (1H, dd, J6b,5 = 7.0 Hz, J6b,6a = 10.0 Hz, H6b),
3.65-3.64 (1H, m, H4), 3.36 (3H, s, OCH3);
13
C NMR (CDCl3, 100 MHz) 
138.40138.27, 129.46, 128.34, 128.33, 128.32, 128.31, 127.75, 127.74, 127.63,
127.57, 127.56, 127.55, 127.04, 95.07, 73.40, 70.99, 69.54, 69.46, 67.21, 55.45;
FAB-MS m/z (rel intens) 341 (M + H+, 1), 91 (100); HRMS (FAB) m/z calcd for
C21H25O4 (M + H+) 341.1747, found 341.1756. Anal. Calcd for C21H24O4; C: 74.09; H:
7.11. Found: C: 74.11; H: 7.14.
Benzyl 4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 6: Pale yellow
oil; IR (CHCl3) 2960, 1496, 1100 cm-1; 1H NMR (CDCl3, 400 MHz)  7.27-7.15 (15H,
m, ArH), 6.04 (1H, dd, J3,4 = 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.91 (1H, dd, J2,1 = 3.2 Hz,
J2,3 = 10.0 Hz, H2), 5.08 (1H, d, J1,2 = 3.2 Hz, H1), 4.73 (1H, d, Ja,b = 11.6 Hz,
CH2Ph), 4.56-4.45 (5H, m, CH2Ph), 4.27-4.23 (1H, m, H5), 3.75 (1H, dd, J6a,5 = 6.4
Hz, J6a,6b = 10.0 Hz, H6a), 3.67-3.63 (2H, m, H4, H6b); 13C NMR (CDCl3, 100 MHz)
 138.33, 137.87, 129.62, 128.35, 128.34, 128.32, 128.31, 128.30, 128.29,
128.20, 128.19, 127.74, 127.73, 127.66, 127.65, 127.56, 127.54, 127.53, 127.12,
93.23, 73.41, 70.98, 69.68, 69.58, 69.55, 67.33; FAB-MS m/z (rel intens) 417 (M +
H+, 1), 91 (100); HRMS (FAB) m/z calcd for C27H29O4 (M + H+) 417.2060, found
417.2064. Anal. Calcd for C27H28O4; C: 77.86; H: 6.78. Found: C: 77.88; H: 6.82.
Allyl 4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 7: Pale yellow oil;
IR (CHCl3) 2985, 1585, 1454, 1101 cm-1; 1H NMR (CDCl3, 400 MHz)  7.27-7.17
(10H, m, ArH), 6.05 (1H, dd, J3,4 = 5.6 Hz, J3,2 = 10.0 Hz, H3), 5.93-5.81 (2H, m, H2,
13
H2’), 5.19 (1H, dd, J3a’,3b’ = 1.6 Hz, J3a’,2’ = 17.2 Hz, H3a’), 5.09 (1H, dd, J3b’,3a’ = 1.6
Hz, J3b’,3a’ = 10.4 Hz, H3b’), 5.03 (1H, d, J1,2 = 3.2 Hz, H1), 4.55 (1H, d, Ja,b = 12.0
Hz, CH2Ph), 4.54 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.49 (1H, d, Ja,b = 11.6 Hz, CH2Ph),
4.47 (1H, d, J = 11.6 Hz, CH2Ph), 4.23-4.17 (1H, m, H1’), 4.02-3.97 (1H, m, H5),
3.75 (1H, dd, J6a,5 = 6.0 Hz, J6a,6b = 10.0 Hz, H6a), 3.70-3.65 (2H, m, H4, H6b); 13C
NMR (CDCl3, 100 MHz)  138.46, 138.33, 134.42, 129.60, 128.33, 128.32, 128.31,
128.30, 127.75, 127.74, 127.73, 127.55, 127.54, 127.53, 127.11, 117.37, 93.31, 73.39,
71.00, 69.54, 69.53, 68.71, 67.31; FAB-MS m/z (rel intens) 367 (M + H+, 5), 91 (100);
HRMS (FAB) m/z calcd for C23H27O4 (M + H+) 367.1904, found 367.1910. Anal.
Calcd for C23H26O4; C: 75.38; H: 7.15. Found: C: 75.39; H: 7.17.
Isopropyl
4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside
8:
Pale
yellow oil; IR (CHCl3) 2972, 1642, 1493, 1094 cm-1; 1H NMR (CDCl3, 400 MHz) 
7.26-7.17 (10H, m, ArH), 6.03 (1H, dd, J3,4 = 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.87 (1H,
dd, J2,1 = 3.2 Hz, J2,3 = 10.0 Hz, H2), 5.13 (1H, d, J1,2 = 3.2 Hz, H1), 4.57-4.46 (4H, m,
CH2Ph), 4.25-4.21 (1H, m, H5), 3.97-3.91 (1H, m, H1’), 3.75 (1H, dd, J6a,5 = 6.0 Hz,
J6a,6b = 10.0 Hz, H6a), 3.69-3.64 (2H, m, H4, H6b), 1.15 (3H, d, J = 6.4 Hz, H2’),
1.09 (3H, d, J = 6.4 Hz, H3’); 13C NMR (CDCl3, 100 MHz)  138.53, 138.36, 130.19,
128.29, 128.28, 128.27, 128.26, 127.72, 127.71, 127.57, 127.49, 127.48, 127.47,
126.77, 92.32, 73.37, 70.96, 69.69, 69.58, 69.27, 67.43, 23.58, 21.84; FAB-MS m/z
(rel intens) 369 (M + H+, 6), 91 (100); HRMS (FAB) m/z calcd for C23H29O4 (M + H+)
369.2060, found 369.2069. Anal. Calcd for C23H28O4; C: 74.97; H: 7.66. Found: C:
74.95; H: 7.62.
Cyclohexyl 4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 9: Pale
yellow oil; IR (CHCl3) 2970, 1510, 1105 cm-1; 1H NMR (CDCl3, 400 MHz) 
7.26-7.17 (10H, m, ArH), 6.03 (1H, dd, J3,4 = 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.89 (1H,
dd, J2,1 = 2.8 Hz, J2,3 = 10.0 Hz, H2), 5.13 (1H, d, J1,2 = 2.8 Hz, H1), 4.57-4.46 (4H, m,
14
CH2Ph), 4.28-4.24 (1H, m, H5), 3.77-3.57 (4H, m, H4, H6, H1’), 1.96-1.83 (2H, m,
H2’), 1.65-1.61 (2H, m, H6’), 1.30-1.09 (6H, m, H3’, H4’, H5’);
13
C NMR (CDCl3,
100 MHz)  138.55, 138.40, 130.35, 128.29, 128.28, 128.27, 128.26, 128.25, 127.70,
127.69, 127.57, 127.44, 127.43, 126.69, 92.24, 75.75, 73.33, 70.88, 69.71, 69.32,
67.50, 33.80, 32.09, 25.63, 24.42, 24.27; FAB-MS m/z (rel intens) 409 (M + H+, 4),
91 (100); HRMS (FAB) m/z calcd for C26H33O4 (M + H+) 409.2373, found 409.2382.
Anal. Calcd for C26H32O4; C: 76.44; H: 7.90. Found: C: 76.48; H: 7.94.
Benzyl 4,6-di-O-methyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 10: Pale yellow
oil; IR (CHCl3) 2989, 1450, 1105 cm-1; 1H NMR (CDCl3, 500 MHz)  7.30-7.18 (5H,
m, ArH), 6.13 (1H, dd, J3,4 = 5.0 Hz, J3,2 = 10.0 Hz, H3), 5.95 (1H, dd, J2,1 = 3.0 Hz,
J2,3 = 10.0 Hz, H2), 5.06 (1H, d, J1,2 = 3.0 Hz, H1), 4.74 (1H, d, J = 11.5 Hz, CH2Ph),
4.50 (1H, d, J = 11.5 Hz, CH2Ph), 4.20-4.17 (1H, m, H5), 3.60 (1H, dd, J6a,5 = 5.5 Hz,
J6a,6b = 10.0 Hz, H6a), 3.51 (1H, dd, J6b,5 = 7.0 Hz, J6b,6a = 10.0 Hz, H6b), 3.44 (1H,
dd, J4,5 = 2.5 Hz, J4,3 = 5.0 Hz, H4), 3.36 (3H, s, OCH3), 3.32 (1H, s, OCH3);
13
C
NMR (CDCl3, 125 MHz) δ 137.88, 129.84, 128.39, 128.38, 128.20, 128.19, 127.69,
126.62, 93.24, 71.79, 69.63, 69.36, 69.04, 59.24, 56.71; FAB-MS m/z (rel intens) 265
(M + H+, 5), 91 (100); HRMS (FAB) m/z calcd for C15H21O4 (M + H+) 265.1434,
found 265.1441. Anal. Calcd for C15H20O4; C: 68.16; H: 7.63. Found: C: 68.18; H:
7.66.
Isopropyl 4,6-di-O-methyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 11: Pale
yellow oil; IR (CHCl3) 2968, 1490, 1105 cm-1; 1H NMR (CDCl3, 500 MHz)  6.11
(1H, dd, J3,4 = 5.0 Hz, J3,2 = 10.0 Hz, H3), 5.90 (1H, dd, J2,1 = 3.0 Hz, J2,3 = 10.0 Hz,
H2), 5.07 (1H, d, J1,2 = 3.0 Hz, H1), 4.17-4.14 (1H, m, H5), 3.96-3.91 (1H, m, H1),
3.58 (1H, dd, J6a,5 = 5.5 Hz, J6a,6b = 10.0 Hz, H6a), 3.52 (1H, dd, J6b,5 = 7.0 Hz, J6b,6a
= 10.0 Hz, H6b), 3.43 (1H, dd, J4,5 = 2.5 Hz, J4,3 = 5.0 Hz, H4), 3.34 (3H, s, OCH3),
3.32 (3H, s, OCH3), 1.17 (3H, d, J = 6.5 Hz, CH3), 1.10 (3H, d, J = 6.5 Hz, CH3); 13C
15
NMR (CDCl3, 125 MHz)  130.38, 126.28, 92.30, 71.85, 69.75, 69.11, 68.91, 59.19,
56.71, 23.56, 21.87; FAB-MS m/z (rel intens) 217 (M + H+, 3), 91 (100); HRMS
(FAB) m/z calcd for C11H21O4 (M + H+) 217.1434, found 217.1440. Anal. Calcd for
C11H20O4; C: 61.09; H: 9.32. Found: C: 61.12; H: 9.35.
Cyclohexyl 4,6-di-O-methyl-2,3-dideoxy-D-threo-hex-2-enopyranoside 12: Pale
yellow oil; IR (CHCl3) 2959, 1550, 1105 cm-1; 1H NMR (CDCl3, 500 MHz)  6.10
(1H, dd, J3,4 = 5.0 Hz, J3,2 = 10.0 Hz, H3), 5.90 (1H, dd, J2,1 = 3.0 Hz, J2,3 = 10.0 Hz,
H2), 5.11 (1H, d, J1,2 = 3.0 Hz, H1), 4.19-4.16 (1H, m, H5), 3.61-3.57 (2H, m, H6a,
H1’), 3.52 (1H, dd, J6b,5 = 7.0 Hz, J6b,6a = 10.0 Hz, H6b), 3.43 (1H, dd, J4,5 = 2.5 Hz,
J4,3 = 5.0 Hz, H4), 3.34 (3H, s, OCH3), 3.32 (3H, s, OCH3), 1.90-1.82 (2H, m, H2’),
1.68-1.66 (2H, m, H6’), 1.33-1.09 (6H, m, H3’, H4’, H5’);
13
C NMR (CDCl3, 125
MHz)  130.48, 126.22, 92.21, 75.74, 71.79, 69.11, 68.90, 59.18, 56.71, 33.77, 32.10,
25.64, 24.44, 24.24; FAB-MS m/z (rel intens) 257 (M + H+, 6), 91 (100); HRMS
(FAB) m/z calcd for C14H25O4 (M + H+) 257.1747, found 257.1749. Anal. Calcd for
C14H24O4; C: 65.60; H: 9.44. Found: C: 65.64; H: 9.45.
p-Methylphenyl-4,6-di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside
33:
Pale yellow oil; IR (CHCl3) 2945, 1605, 1408, 1099 cm-1; 1H NMR (CDCl3, 500 MHz)
 7.25-7.14 (10H, m, ArH), 6.99-6.93 (4H, m, ArH), 6.18-6.15 (1H, m, H3), 6.04 (1H,
dd, J2,1 = 3.0 Hz, J2,3 = 10.0 Hz, H2), 5.63 (1H, d, J1,2 = 3.0 Hz, H1), 4.58 (1H, d, J =
12.0 Hz, CH2Ph), 4.52 (1H, d, J = 12.0 Hz, CH2Ph), 4.45 (1H, d, J = 11.5 Hz, CH2Ph),
4.41 (1H, d, J = 11.5 Hz, CH2Ph), 4.36-4.33 (1H, m, H5), 3.79 (1H, dd, J6a,5 = 6.5 Hz,
J6a,6b = 10.0 Hz, H6a), 3.74 (1H, dd, J4,5 = 2.5 Hz, J4,3 = 5.5 Hz, H4), 3.65 (1H, dd,
J6b,5 = 6.5 Hz, J6b,6a = 10.0 Hz, H6b), 2.21 (3H, s, CH3); 13C NMR (CDCl3, 125 MHz)
 155.19, 138.35, 138.22, 131.56, 129.88, 129.87, 128.77, 128.38, 128.37, 128.26,
128.25, 127.85, 127.83, 127.82, 127.72, 127.63, 127.62, 127.49, 127.23, 127.22,
93.22, 73.35, 71.28, 70.28, 69.25, 67.06, 20.56.
16
Typical
Procedure
of
Glycosylation
for
Preparing
2,3-Unsaturated
Glycopyranoside Derivatives 17-23. To a solution of endo-galactal 1 (1.0 equiv.) in
anhydrous CH2Cl2 (1.5 mL) was added diethyl phosphorochloridite (1.2 equiv.) and
Et3N (3.0 equiv.). The reaction mixture was stirred at 0 C under N2 for 30 min. After
the phosphanylation was completed, one equivalent of AlCl3 and three equivalents of
an sugar alcohol substrate were added into the reaction mixture and stirred at 0 C for
30 min. Once the reaction was completed, the resulting solution was added to CH2Cl2
(50 mL), washed with H2O (20 mL × 2), and brine (20 mL × 2). The organic layer
was concentrated under reduced pressure and purified by column chromatography on
silica gel (33% EtOAc in hexanes as eluant) to give 2,3-unsaturated glycopyranosides
17-23 in 81–86 % yields.
4,6-Di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside-(16)-1,2:3,4-di-Oisopropylidene-D-galactopyranoside 17: Pale yellow oil; IR (CHCl3) 2922, 1643,
1463, 1168 cm-1; 1H NMR (CDCl3, 400 MHz)  7.26-7.18 (10H, m, ArH), 6.02 (1H,
dd, J3,4 = 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.90 (1H, dd, J2,1 = 2.8 Hz, J2,3 = 10.0 Hz, H2),
5.43 (1H, d, J1’,2’ = 5.2 Hz, H1’), 5.04 (1H, d, J1,2 = 2.8 Hz, H1), 4.57-4.45 (5H, m,
H3’, CH2Ph), 4.23-4.18 (3H, m, H5, H2’, H4’), 3.99-3.95 (1H, m, H5’), 3.80-3.61
(5H, m, H4, H6, H6’), 1.44 (3H, s, CH3), 1.35 (3H, s, CH3), 1.26 (3H, s, CH3), 1.24
(3H, s, CH3); 13C NMR (CDCl3, 100 MHz)  138.46, 138.26, 129.43, 128.29, 128.28,
128.26, 128.25, 127.72, 127.71, 127.61, 127.60, 127.55, 127.47, 126.97, 109.18,
108.48, 96.30, 94.48, 73.35, 71.11, 70.83, 70.63, 70.60, 69.45, 69.14, 67.11, 66.60,
65.91, 26.04, 25.93, 24.89, 24.49; FAB-MS m/z (rel intens) 569 (M + H+, 1), 253 (6),
181 (22), 91 (100); HRMS (FAB) m/z calcd for C32H41O9 (M + H+) 569.2745, found
569.2755. Anal. Calcd for C32H40O9; C: 67.59; H: 7.09. Found: C: 67.63; H: 7.12.
4,6-Di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside-(16)-1,2,3,4-tetraO-methyl-D-glucopyranoside 18: Pale yellow oil; IR (CHCl3) 2918, 1641, 1453,
17
1100 cm-1; 1H NMR (CDCl3, 400 MHz)  7.26-7.18 (10H, m, ArH), 6.03 (1H, dd, J3,4
= 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.90 (1H, dd, J2,1 = 2.8 Hz, J2,3 = 10.0 Hz, H2), 5.07
(1H, d, J1,2 = 2.8 Hz, H1), 4.70 (1H, d, J1’,2’ = 3.6 Hz, H1’), 4.57-4.47 (4H, m, CH2Ph),
4.20-4.16 (1H, m, H5), 3.92 (1H, dd, J6a’,5’ = 4.0 Hz, J6a’,6b’ = 11.2 Hz, H6a’), 3.75
(1H, dd, J6a,5 = 6.4 Hz, J6a,6b = 10.0 Hz, H6a), 3.67-3.60 (3H, m, H4, H6b, H6b’),
3.54-3.50 (4H, m, H5’, OCH3), 3.44-3.39 (7H, m, H3’, 2xOCH3), 3.31 (3H, s, OCH3),
3.12-3.07 (2H, m, H2’, H4’);
13
C NMR (CDCl3, 50 MHz)  138.46, 138.25, 129.43,
128.29, 128.28, 128.26, 128.25, 127.72, 127.71, 127.61, 127.60, 127.55, 127.47,
126.97, 109.18, 108.48, 96.30, 94.48, 73.35, 71.11, 70.83, 70.63, 70.60, 69.45, 69.14,
67.11, 66.60, 65.91, 26.04, 25.93, 24.89, 24.49; LRMS (EI) m/z (rel intens) 544 (M+,
1), 394 (11), 91 (100); HRMS (EI) m/z calcd for C30H40O9 (M+) 544.2672, found
544.2676. Anal. Calcd for C30H40O9; C: 66.16; H: 7.40. Found: C: 66.19; H: 7.45.
4,6-Di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside-(16)-1-methyl-2,3,4tri-O-benzyl-D-glucopyranoside 19: Pale yellow oil; IR (CHCl3) 2920, 1643, 1454,
1099 cm-1; 1H NMR (CDCl3, 400 MHz)  7.28-7.14 (25H, m, ArH), 6.01 (1H, dd, J3,4
= 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.91 (1H, dd, J2,1 = 2.8 Hz, J2,3 = 10.0 Hz, H2), 5.06
(1H, d, J1,2 = 2.8 Hz, H1), 4.88 ( 1H, d, Ja,b = 10.8 Hz, CH2Ph), 4.76 ( 1H, d, Ja,b =
10.8 Hz, CH2Ph), 4.71 ( 1H, d, Ja,b = 10.8 Hz, CH2Ph), 4.69 ( 1H, d, Ja,b = 12.0 Hz,
CH2Ph), 4.58 ( 1H, d, Ja,b = 10.8 Hz, CH2Ph), 4.57 ( 1H, d, Ja,b = 12.0 Hz, CH2Ph),
4.53 (1H, d, J1’,2’ = 3.6 Hz, H1’), 4.51 ( 1H, d, Ja,b = 10.8 Hz, CH2Ph), 4.45 ( 1H, d,
Ja,b = 10.8 Hz, CH2Ph), 4.37 ( 1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.31 ( 1H, d, Ja,b = 12.0
Hz, CH2Ph), 4.17-4.14 (1H, m, H5), 3.98 (1H, dd, J6a’,5’ = 3.6 Hz, J6a’,6b’ = 11.2 Hz,
H6a’), 3.90 (1H, dd, J3’,4’ = 9.6 Hz, J3’,2’ = 9.6 Hz, H3’), 3.72-3.62 (4H, m, H4, H6a,
H5’, H6b’), 3.57-3.48 (2H, m, H4’, H6b), 3.43 (1H, dd, J2’,1’ = 3.6 Hz, J2’,3’ = 9.6 Hz,
H2’), 3.28 (3H, s, OCH3);
13
C NMR (CDCl3, 50 MHz)  138.39, 138.34, 138.15,
138.14, 129.45, 128.41, 128.40, 128.39, 128.36, 128.35, 128.34, 128.33, 128.29,
18
128.28, 128.27, 128.02, 128.01, 127.89, 127.88, 127.87, 127.74, 127.73, 127.72,
127.71, 127.59, 127.52, 127.51, 127.50, 126.87, 98.01, 94.53, 81.97, 79.86, 77.77,
75.69, 74.94, 73.28, 73.27, 71.07, 70.00, 69.57, 69.08, 66.97, 66.64, 55.11; FAB-MS
m/z (rel intens) 795 (M + Na+, 2), 105 (32), 191 (100); HRMS (FAB) m/z calcd for
C48H52NaO9 (M + Na+) 795.3504, found 795.3507. Anal. Calcd for C48H52O9; C:
74.59; H: 6.78. Found: C: 74.66; H: 6.84.
4,6-Di-O-benzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside-(13)-1,2:5,6-di-Oisopropylidene-D-glucofuranoside 20: Pale yellow oil; IR (CHCl3) 2926, 1646, 1463,
1095 cm-1; 1H NMR (CDCl3, 400 MHz)  7.27-7.17 (10H, m, ArH), 6.05 (1H, dd, J3,4
= 5.2 Hz, J3,2 = 10.0 Hz, H3), 5.89 (1H, dd, J2,1 = 2.4 Hz, J2,3 = 10.0 Hz, H2), 5.76
(1H, d, J1’,2’ = 3.6 Hz, H1’), 5.23 (1H, d, J1,2 = 2.4 Hz, H1), 4.73 (1H, d, J2’,1’ = 3.6 Hz,
H2’), 4.56 ( 1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.54 ( 1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.48
( 1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.44 ( 1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.23 (1H, d, J3’,4’
= 2.8 Hz, H3’), 4.18-4.12 (2H, m, H5, H5’), 4.04-3.99 (2H, m, H4’, H6b’), 3.89 (1H,
dd, J6a’,5’ = 5.6 Hz, J6a’,6b’ = 8.4 Hz, H6a’), 3.71 (1H, d, J6,5 = 6.0 Hz, H6), 3.63 (1H,
dd, J4,5 = 2.4 Hz, J4,3 = 5.2 Hz, H4), 1.39 (3H, s, CH3), 1.33 (3H, s, CH3), 1.25 (3H, s,
CH3), 1.09 (3H, s, CH3);
13
C NMR (CDCl3, 50 MHz)  138.23, 138.22, 129.16,
128.38, 128.37, 128.36, 128.35, 127.75, 127.74, 127.73, 127.60, 127.59, 127.58,
127.04, 111.76, 109.03, 105.38, 95.71, 83.92, 81.41, 81.23, 73.66, 72.70, 70.90, 70.37,
69.96, 67.70, 67.29, 26.88, 26.82, 26.09, 25.39; FAB-MS m/z (rel intens) 569 (M +
H+, 3), 91 (100); HRMS (FAB) m/z calcd for C32H41O9 (M + H+) 569.2745, found
569.2746. Anal. Calcd for C32H40O9; C: 67.59; H: 7.09. Found: C: 67.61; H: 7.12.
4,6-Di-O-p-mthoxybenzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside-(16)-1,2:3,
4-di-O- isopropylidene-D-galactopyranoside 21: Pale yellow oil; IR (CHCl3) 2952,
1645, 1464, 1170
cm-1; 1H NMR (CDCl3, 500 MHz)  7.18 (2H, d, J = 7.5 Hz, ArH),
7.12 (2H, d, J = 7.5 Hz, ArH), 6.79 (2H, d, J = 7.5 Hz, ArH), 6.75 (2H, d, J = 7.5 Hz,
19
ArH), 5.98 (1H, dd, J3,4 = 5.5 Hz, J3,2 = 10.0 Hz, H3), 5.88 (1H, dd, J2,1 = 4.0 Hz, J2,3
= 10.0 Hz, H2), 5.43 (1H, d, J1,2 = 4.0 Hz, H1), 5.03 (1H, brs, H1’), 4.50-4.39 (5H, m,
CH2Ph, H4’), 4.23-4.16 (3H, m, H2’, H3’, H5), 3.97-3.95 (1H, m, H5’), 3.79-3.68
(9H, m, H6’, H6a, OCH3), 3.60-3.57 (2H, m, H4, H6b), 1.44 (3H, s, CH3), 1.36 (3H, s,
CH3), 1.26 (3H, s, CH3), 1.24 (3H, s, CH3);
13
C NMR (CDCl3, 125 MHz)  159.19,
159.15, 130.59, 130.38, 129.40, 129.39, 129.33, 129.32, 129.21, 127.19, 113.77,
113.76, 113.71, 113.70, 109.21, 108.53, 96.33, 94.53, 73.03, 70.88, 70.84, 70.65,
70.61, 69.46, 68.82, 66.75, 66.60, 65.92, 55.23, 55.22, 26.08, 25.97, 24.93, 24.51;
FAB-MS m/z (rel intens) 629 (M + H+, 3), 91 (100); HRMS (FAB) m/z calcd for
C34H45O11 (M + H+) 629.2956, found 629.2961. Anal. Calcd for C34H44O11; C: 64.95;
H: 7.05. Found: C: 64.98; H: 7.07.
4,6-Di-O-p-mthoxybenzyl-2,3-dideoxy-D-threo-hex-2-enopyranoside-(16)-1-met
hyl-2,3,4-tri-O-benzyl-D-glucopyranoside 22: Pale yellow oil; IR (CHCl3) 2920,
1640, 1501, 1109 cm-1; 1H NMR (CDCl3, 500 MHz)  7.26-7.17 (15H, m, ArH),
7.11-7.09 (2H, m, ArH), 7.07-7.05 (2H, m, ArH), 6.75-6.72 (4H, m, ArH), 5.98-5.96
(1H, m, H3), 5.90-5.87 (1H, m, H2), 5.04 (1H, brs, H1), 4.87 ( 1H, d, Ja,b = 11.0 Hz,
CH2Ph), 4.75 ( 1H, d, Ja,b = 11.0 Hz, CH2Ph), 4.71 ( 1H, d, Ja,b = 11.0 Hz, CH2Ph),
4.69 ( 1H, d, Ja,b = 11.0 Hz, CH2Ph), 4.59-4.56 ( 2H, m, CH2Ph), 4.53 (1H, brs, H1’),
4.44 ( 1H, d, Ja,b = 11.0 Hz, CH2Ph), 4.38 ( 1H, d, Ja,b = 11.0 Hz, CH2Ph), 4.30 ( 1H,
d, Ja,b = 12.0 Hz, CH2Ph), 4.24 ( 1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.11 (1H, brs, H5),
3.98-3.96 (1H, m, H5’), 3.91-3.88 (1H, m, H3’), 3.70-3.64 (9H, m, H6’, H6a, OCH3),
3.58 (1H, brs, H4), 3.51-3.42 (3H, m, H4’, H2’, H6b), 3.28 (3H, s, OCH3); 13C NMR
(CDCl3, 125 MHz)  159.18, 159.09, 138.81, 138.39, 138.19, 130.56, 130.31, 129.38,
129.37, 129.25, 129.20, 129.19, 128.42, 128.41, 128.40, 128.37, 128.36, 128.34,
128.33, 128.32, 128.04, 128.03, 127.90, 127.89, 127.85, 127.77, 127.76, 127.63,
127.51, 127.05, 113.70, 113.69, 98.04, 94.57, 82.00, 79.92, 77.81, 75.70, 74.96, 73.31,
20
72.97, 70.82, 70.03, 69.61, 68.81, 66.66, 66.65, 55.23, 55.22, 55.13; FAB-MS m/z (rel
intens) 833 (M + H+, 4), 91 (100); HRMS (FAB) m/z calcd for C50H57O11 (M + H+)
833.3895, found 8.33.3897. Anal. Calcd for C50H56O11; C: 72.10; H: 6.78. Found: C:
72.15; H: 6.84.
Typical Glycosylation Procedure (synthesis of 23). To a solution of exo-galactal 2
(1.0 equiv.) in anhydrous CH2Cl2 (1.5 mL) was added diethyl phosphorochloridite
(1.2 equiv.) and Et3N (3.0 equiv.). The reaction mixture was stirred at 0 C under N2
for 30 min. After the phosphanylation was completed, one equivalent of AlCl3 and
three equivalents of methanol were added into the reaction mixture and stirred at 0 C
for 30 min. Once the reaction was completed, the resulting solution was added to
CH2Cl2 (50 mL), washed with H2O (20 mL × 2), and brine (20 mL × 2). The organic
layer was concentrated under reduced pressure and purified by column
chromatography on silica gel (15% EtOAc in hexanes as eluant) to give 23 in 85 %
yields.
Methyl 4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-enopyranoside
23: IR (CHCl3) 2960, 1642, 1493, 1094 cm-1; 1H NMR (CDCl3, 400 MHz) 
7.28-7.17 (20H, m, ArH), 5.77 (1H, dd, J1’,2b’ = 10.8 Hz, J1’,2a’ = 17.6 Hz, H1’), 5.43
(1H, dd, J2a’,2b’ = 2.0 Hz, J2a’,1’ = 17.6 Hz, H2a’), 5.21 (1H, dd, J2b’,2a’ = 2.0 Hz, J2b’,1’
= 10.8 Hz, H2b’), 4.88 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.77 (1H, d, Ja,b = 10.8 Hz,
CH2Ph), 4.69 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.64 (1H, d, Ja,b = 11.6 Hz, CH2Ph),
4.54 (1H, d, Ja,b = 10.8 Hz, CH2Ph), 4.53 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.43 (1H, d,
Ja,b = 12.0 Hz, CH2Ph), 4.37 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 3.97 (1H, dd, J3,4 = 2.8
Hz, J3,2 = 10.0 Hz, H3), 3.90 (1H, dd, J4,5 = 0.8 Hz, J4,3 = 2.8 Hz, H4), 4.06-4.03 (1H,
m, H5), 3.94 (1H, brs, H4), 3.72 (1H, d, J2,3 = 9.6 Hz, H2), 3.79-3.72 (2H, m, H2, H5),
3.56 (1H, dd, J6a,5 = 6.8 Hz, J6a,6b = 9.6 Hz, H6a), 3.51 (1H, dd, J6b,5 = 6.0 Hz, J6b,6a =
9.6 Hz, H6b), 3.07 (3H, s, OCH3);
13
C NMR (CDCl3, 100 MHz)  138.93, 138.71,
21
138.18, 138.09, 134.64, 128.64, 128.63, 128.62, 128.35, 128.34, 128.33, 128.32,
128.14, 128.13, 128.12, 128.11, 127.98, 127.97, 127.96, 127.69, 127.68, 127.67,
127.64, 127.63, 127.55, 127.48, 127.47, 127.46, 127.45, 118.99, 100.01, 80.49, 80.31,
76.05, 75.09, 74.47, 73.46, 73.01, 70.36, 69.12, 49.07; FAB-MS m/z (rel intens) 581
(M + H+, 4), 91 (100); HRMS (FAB) m/z calcd for C37H41O6 (M + H+) 581.2898,
found 581.2902. Anal. Calcd for C37H40O6; C: 76.53; H: 6.94. Found: C: 76.59; H:
6.97.
n-Butyl
4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-
enopyranoside 24: IR (CHCl3) 2950, 1641, 1453, 1090 cm-1; 1H NMR (CDCl3, 400
MHz)  7.27-7.18 (20H, m, ArH), 5.82 (1H, dd, J1’,2b’ = 10.8 Hz, J1’,2a’ = 17.6 Hz,
H1’), 5.41 (1H, dd, J2a’,2b’ = 2.0 Hz, J2a’,1’ = 17.6 Hz, H2a’), 5.14 (1H, dd, J2b’,2a’ = 2.0
Hz, J2b’,1’ = 10.8 Hz, H2b’), 4.87 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.79 (1H, d, Ja,b =
11.6 Hz, CH2Ph), 4.68 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.64 (1H, d, Ja,b = 11.6 Hz,
CH2Ph), 4.55 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.53 (1H, d, Ja,b = 11.6 Hz, CH2Ph),
4.43 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.38 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.00 (1H, dd,
J3,4 = 2.8 Hz, J3,2 = 10.0 Hz, H3), 3.92 (1H, dd, J4,5 = 1.2 Hz, J4,3 = 2.8 Hz, H4),
3.82-3.79 (1H, m, H5), 3.75 (1H, d, J2,3 = 10.0 Hz, H2), 3.56 (1H, dd, J6a,5 = 7.2 Hz,
J6a,6b = 9.6 Hz, H6a), 3.50 (1H, dd, J6b,5 = 6.0 Hz, J6b,6a = 9.6 Hz, H6b), 3.33-3.19 (2H,
m, H1”), 1.50-1.45 (2H, m, H2”), 1.26-1.18 (2H, m, H3”), 0.81 (3H, t, J4”,3” = 7.2 Hz,
H4”); 13C NMR (CDCl3, 100 MHz)  139.02, 138.80, 138.57, 138.19, 135.71, 128.37,
128.36, 128.35, 128.31, 128.30, 128.29, 128.17, 128.16, 128.15, 128.11, 128.10,
127.99, 127.98, 127.74, 127.73, 127.72, 127.47, 127.46, 127.44, 127.43, 118.30,
99.87, 80.64, 80.35, 75.65, 75.06, 74.47, 73.44, 72.86, 70.30, 69.15, 61.60, 31.83,
19.57, 13.97; FAB-MS m/z (rel intens) 623 (M + H+, 3), 91 (100); HRMS (FAB) m/z
calcd for C40H47O6 (M + H+) 623.3367, found 623.3373. Anal. Calcd for C40H46O6; C:
77.14; H: 7.44. Found: C: 77.19; H: 7.48.
22
n-Hexyl
4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-
enopyranoside 25: IR (CHCl3) 2958, 1640, 1498, 1100 cm-1; 1H NMR (CDCl3, 400
MHz)  7.26-7.17 (20H, m, ArH), 5.77 (1H, dd, J1’,2b’ = 10.8 Hz, J1’,2a’ = 17.6 Hz,
H1’), 5.41 (1H, dd, J2a’,2b’ = 2.0 Hz, J2a’,1’ = 17.6 Hz, H2a’), 5.14 (1H, dd, J2b’,2a’ = 2.0
Hz, J2b’,1’ = 10.8 Hz, H2b’), 4.87 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.79 (1H, d, Ja,b =
11.6 Hz, CH2Ph), 4.68 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.64 (1H, d, Ja,b = 11.6 Hz,
CH2Ph), 4.55 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.53 (1H, d, Ja,b = 11.6 Hz, CH2Ph),
4.43 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.37 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.00 (1H, dd,
J3,4 = 2.8 Hz, J3,2 = 10.0 Hz, H3), 3.92 (1H, dd, J4,5 = 1.6 Hz, J4,3 = 2.8 Hz, H4),
3.82-3.79 (1H, m, H5), 3.75 (1H, d, J2,3 = 10.0 Hz, H2), 3.56 (1H, dd, J6a,5 = 7.2 Hz,
J6a,6b = 9.6 Hz, H6a), 3.50 (1H, dd, J6b,5 = 6.0 Hz, J6b,6a = 9.6 Hz, H6b), 3.32-3.18 (2H,
m, H1”), 1.51-1.46 (2H, m, H2”), 1.25-1.17 (6H, m, H3”, H4”, H5”), 0.79 (3H, t, J6”,5”
= 7.2 Hz, H6”);
13
C NMR (CDCl3, 100 MHz)  139.02, 138.81, 138.77, 138.20,
135.74, 128.28, 128,27, 128.26, 128.25, 128.14, 128.13, 128.12, 128.11, 128.10,
128.09, 127.99, 127.98, 127.97, 127.66, 127.65, 127.43, 127.42, 127.41, 127.40,
127.39, 118.28, 99.90, 80.64, 80.35, 75.62, 75.09, 74.46, 73.44, 72.85, 70.32, 69.18,
61.91, 31.66, 29.68, 25.98, 22.61, 14.04; FAB-MS m/z (rel intens) 651 (M + H+, 5),
91 (100); HRMS (FAB) m/z calcd for C42H51O6 (M + H+) 651.3680, found 651.3682.
Anal. Calcd for C42H50O6; C: 77.51; H: 7.74. Found: C: 77.54; H: 7.79.
Allyl
4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-enopyranoside
26: IR (CHCl3) 2960, 1642, 1493, 1094 cm-1; 1H NMR (CDCl3, 400 MHz)  7.36–
7.25 (20H, m, ArH), 5.98–5.87 (2H, m, H1’, H2”), 4.52 (1H, dd, J2a’,1’ = 17.6 Hz,
J2a’,2b’ = 1.6 Hz, H2a’), 5.25 (1H, dd, J3a”,2” = 11.6 Hz, J3a”,3b” = 1.6 Hz, H3a”), 5.22
(1H, dd, J2b’,1’ = 17.6 Hz, J2b’,2a’ = 1.6 Hz, H2b’), 5.08 (1H, dd, J3b”,2” = 10.4 Hz,
H3b”), 4.95 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.87 (1H, d, Ja,b = 11.2 Hz, CH2Ph), 4.75
(1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.72 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.63 (1H, d, Ja,b =
23
11.2 Hz, CH2Ph), 4.60 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.49 (1H, d, Ja,b = 12.0 Hz,
CH2Ph), 4.45 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 3.99–3.83 (5H, m, H2, H4, H5, H6a,
H6b), 3.64–3.55 (2H, m, H1a”, H1b”); 13C NMR (CDCl3, 100 MHz)  138.99, 138.77,
138.45, 138.17, 135.26, 135.11, 128.40, 128,39, 128.38, 128.37, 128.36, 128.19,
128.18, 128.17, 128.16, 128.15, 128.02, 128.01, 127.69, 127.68, 127.67, 127.49,
127.48, 127.47, 127.46, 127.45, 118.65, 116.30, 100.25, 80.39, 75.76, 75.04, 74.51,
73.41, 72.91, 70.45, 69.02, 63.06; FAB-MS m/z (rel intens) 607 (M + H+, 7), 91 (100);
HRMS (FAB) m/z calcd for C39H43O6 (M + H+) 607.3054, found 607.3061. Anal.
Calcd for C39H42O6; C: 77.20; H: 6.98. Found: C: 77.24; H: 6.73.
Benzyl
4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-
enopyranoside 27: IR (CHCl3) 2950, 1651, 1503, 1102 cm-1; 1H NMR (CDCl3, 400
MHz)  7.25-7.16 (25H, m, ArH), 5.91 (1H, dd, J1’,2b’ = 10.8 Hz, J1’,2a’ = 17.6 Hz,
H1’), 5.51 (1H, dd, J2a’,2b’ = 2.0 Hz, J2a’,1’ = 17.6 Hz, H2a’), 5.21 (1H, dd, J2b’,2a’ = 2.0
Hz, J2b’,1’ = 10.8 Hz, H2b’), 4.86 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.82 (1H, d, Ja,b =
11.2 Hz, CH2Ph), 4.66 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.63 (1H, d, Ja,b = 11.6 Hz,
CH2Ph), 4.57 (1H, d, Ja,b = 11.2 Hz, CH2Ph), 4.52 (1H, d, Ja,b = 11.6 Hz, CH2Ph),
4.44 (1H, d, Ja,b = 12.8 Hz, CH2Ph), 4.38-4.32 (3H, m, CH2Ph), 4.04 (1H, dd, J3,4 =
2.8 Hz, J3,2 = 10.0 Hz, H3), 3.90 (1H, dd, J4,5 = 1.2 Hz, J4,3 = 2.8 Hz, H4), 3.81 (1H, d,
J2,3 = 10.0 Hz, H2), 3.79-3.76 (1H, m, H5), 3.53 (1H, dd, J6a,5 = 7.2 Hz, J6a,6b = 9.6 Hz,
H6a), 3.43 (1H, dd, J6b,5 = 6.0 Hz, J6b,6a = 9.6 Hz, H6b); 13C NMR (CDCl3, 100 MHz)
 139.02, 138.89, 138.74, 138.68, 138.18, 135.41, 128.35, 128,34, 128.29, 128.28,
128.17, 128.16, 128.15, 128.14, 128.13, 128.12, 128.11, 128.10, 127.98, 127.97,
127.69, 127.68, 127.61, 127.49, 127.48, 127.47, 127.46, 127.42, 127.41, 127.40,
127.01, 118.84, 100.54, 80.62, 80.20, 75.56, 74.98, 74.48, 73.36, 72.80, 70.53, 68.99,
63.78; FAB-MS m/z (rel intens) 657 (M + H+, 3), 91 (100); HRMS (FAB) m/z calcd
for C43H45O6 (M + H+) 657.3211, found 657.3214. Anal. Calcd for C43H44O6; C:
24
78.63; H: 6.75. Found: C: 78.65; H: 6.78.
Isopropyl
4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-
enopyranoside 28: IR (CHCl3) 2935, 1635, 1498, 1090 cm-1; 1H NMR (CDCl3, 400
MHz)  7.26-7.17 (20H, m, ArH), 5.95 (1H, dd, J1’,2b’ = 10.8 Hz, J1’,2a’ = 17.6 Hz,
H1’), 5.44 (1H, dd, J2a’,2b’ = 2.0 Hz, J2a’,1’ = 17.6 Hz, H2a’), 5.11 (1H, dd, J2b’,2a’ = 2.0
Hz, J2b’,1’ = 10.8 Hz, H2b’), 4.86 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.83 (1H, d, Ja,b =
11.2 Hz, CH2Ph), 4.68 (2H, brs, CH2Ph), 4.54 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.52
(1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.43 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.39 (1H, d, Ja,b =
12.0 Hz, CH2Ph), 4.02-3.95 (3H, m, H3, H4, H5), 3.93-3.85 (1H, m, H1”), 3.71 (1H,
d, J2,3 = 10.0 Hz, H2), 3.58 (1H, dd, J6a,5 = 7.6 Hz, J6a,6b = 9.6 Hz, H6a), 3.50 (1H, dd,
J6b,5 = 6.0 Hz, J6b,6a = 9.6 Hz, H6b), 1.09 (1H, d, J = 2.4 Hz, H2”), 1.07 (1H, d, J =
2.4 Hz, H3”); 13C NMR (CDCl3, 100 MHz)  139.03, 138.78, 138.70, 138.15, 136.47,
128.37, 128,36, 128.29, 128.28, 128.15, 128.14, 128.13, 128.12, 127.94, 127.93,
127.90, 127.89, 127.64, 127.63, 127.62, 127.39, 127.38, 127.37, 127.36, 127.33,
117.45, 100.17, 81.08, 80.45, 75.56, 74.65, 74.34, 73.41, 72.59, 70.22, 69.00, 65.27,
24.17, 23.06; FAB-MS m/z (rel intens) 609 (M + H+, 4), 91 (100); HRMS (FAB) m/z
calcd for C39H45O6 (M + H+) 609.3211, found 609.3215. Anal. Calcd for C39H44O6; C:
76.95; H: 7.29. Found: C: 76.98; H: 7.31.
Cyclohexyl
4,5,6,8-tetra-O-benzyl-1,2-dideoxy-α-D-galacto-oct-3-ulo-1-
enopyranoside 29: IR (CHCl3) 2945, 1632, 1499, 1104 cm-1; 1H NMR (CDCl3, 400
MHz)  7.28-7.16 (20H, m, ArH), 6.96 (1H, dd, J1’,2b’ = 11.2 Hz, J1’,2a’ = 17.6 Hz,
H1’), 5.46 (1H, dd, J2a’,2b’ = 2.4 Hz, J2a’,1’ = 17.6 Hz, H2a’), 5.10 (1H, dd, J2b’,2a’ = 2.4
Hz, J2b’,1’ = 11.2 Hz, H2b’), 4.87 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.84 (1H, d, Ja,b =
12.0 Hz, CH2Ph), 4.67 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.64 (1H, d, Ja,b = 12.0 Hz,
CH2Ph), 4.54 (1H, d, Ja,b = 11.6 Hz, CH2Ph), 4.53 (1H, d, Ja,b = 11.6 Hz, CH2Ph),
4.44 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.39 (1H, d, Ja,b = 12.0 Hz, CH2Ph), 4.05-4.02
25
(1H, m, H5), 3.98 (1H, dd, J3,4 = 1.6 Hz, J3,2 = 9.6 Hz, H3), 3.94 (1H, dd, J4,5 = 0.8 Hz,
J4,3 = 2.4 Hz, H4), 3.70 (1H, d, J2,3 = 9.6 Hz, H2), 3.58 (1H, dd, J6a,5 = 7.2 Hz, J6a,6b =
9.6 Hz, H6a), 3.55-3.47 (2H, m, H6b, H1”), 1.78-1.71 (2H, m, H2”), 1.63-1.59 (2H,
m, H6”), 1.35-1.05 (6H, m, H6b, H3”, H4”, H5”);
13
C NMR (CDCl3, 50 MHz) 
139.14, 138.85, 138.28, 136.70, 128.29, 128.28, 128.27, 128.14, 128.13, 128.12,
128.11, 128.10, 127.87, 127.81, 127.80, 127.61, 127.60, 127.59, 127.58, 127.39,
127.38, 127.37, 127.36, 127.35, 117.39, 100.30, 81.31, 80.37, 75.37, 74.90, 74.37,
73.41, 72.63, 71.48, 70.34, 69.14, 34.18, 33.88, 25.56, 24.87, 24.65; FAB-MS m/z (rel
intens) 649 (M + H+, 3), 91 (100); HRMS (FAB) m/z calcd for C42H49O6 (M + H+)
649.3524, found 649.3527. Anal. Calcd for C42H48O6; C: 77.75; H: 7.46. Found: C:
77.78; H: 7.48.
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Yen-Bo Chen, Su-I Wang, Zi-Ping Lin, Chun-Hung Lin, Min-Tsang Hsieh and
Hui-Chang Lin*
Stereoselective Glycosylation of D-Galactals by Diethyl
Phosphorochloridite- and AlCl3-assisted Ferrier Rearrangement
32