Synthesis of 4-O-D-mannopyranosyl-α-D-glucopyranosides by intramolecular glycosylation of 6-O-tethered mannosyl donors

Article abstract of DOI:10.1016/S0040-4020(99)01053-4

A series of mannosyl donors linked via position 6 by a carbonate, oxalate, malonate, succinate, and phthalate tether, respectively, to position 3 of a glucoside and glucosamine acceptor afforded during intramolecular glycosylation, anomeric mixture of the corresponding disaccharides. The dependence of the diastereoselectivity on the glycosylation procedure, the solvent, and the blocking groups in comparison to an intermolecular mannosylation is studied. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(99)01053-4

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 563–579
Synthesis of 4-O-d-Mannopyranosyl-a-d-glucopyranosides by
Intramolecular Glycosylation of 6-O-Tethered Mannosyl Donors
*
Gregor Lemanski and Thomas Ziegler
Institute of Organic Chemistry, University of Cologne, Greinstraße 4, D-50939 Cologne, Germany
Received 29 October 1999; accepted 3 December 1999
Abstract—A series of mannosyl donors linked via position 6 by a carbonate, oxalate, malonate, succinate, and phthalate tether, respectively,
to position 3 of a glucoside and glucosamine acceptor afforded during intramolecular glycosylation, anomeric mixture of the corresponding
disaccharides. The dependence of the diastereoselectivity on the glycosylation procedure, the solvent, and the blocking groups in comparison
to an intermolecular mannosylation is studied. ᭧ 2000 Elsevier Science Ltd. All rights reserved.
Introduction
Thus, a suitably protected mannosyl donor was first linked
by a succinyl or malonyl tether at its position 6 to a glucosyl
acceptor followed by intramolecular glycosylation/cyclisa-
tion to afford the corresponding disaccharides (Scheme 1).8,9
The disaccharide fragment b-d-Manp-(1!4)-d-Glcp/
GlcNAcp is a very common structural disaccharide motif
found in a huge number of naturally occurring oligo-
saccharides. For example, the Complex Carbohydrate
Structure Database (CCSD) at the University of Georgia
(http://128.192.9.29/carbbank/) contains more than 7,000
entries for this disaccharide fragment. In particular, this
structure is found in the core region of N-glycanes of glyco-
proteins, in glycosphingolipids, and in various lipopoly-
saccharides. Without any doubt, it can be regarded as one
of the most significant disaccharide structures found in
nature. Due to the importance of b-d-Manp-(1!4)-d-
Glcp/GlcNAcp fragments significant efforts toward the
chemical synthesis of that structure have been undertaken
in recent years and novel approaches for the construction of
the difficult b-mannosidic linkage have been developed.1–7
For the disaccharide d-Manp-(1!4)-d-Glcp an a/b-ratio of
64:36 was obtained9 whereas the disaccharide b-d-Manp-
(1!4)-d-GlcNAcp was exclusively formed.8 In order to
understand the factors which influence the anomeric
outcome of these intramolecular mannosylations we now
made systematic variations of the length and flexibility
of the tether as well as variations of the leaving group
of the donor. Furthermore, solvent effects and different
activation procedures have been studied in relation to
the diastereoselectivity of intramolecular mannosylations
as well.
Results and Discussion
Recently, we disclosed a new procedure for the synthesis of
b-d-mannose containing saccharides using the intramolecu-
lar glycosylation approach via prearranged glycosides.8
As a basis for the comparison of the diastereoselectivity of
intramolecular glycosylations and of the factors which may
Scheme 1. Intramolecular glycosylation with 6-O-tethered mannosyl donors.
Keywords: intermolecular glycosylation; diastereoselectivity.
* Corresponding author. Fax: ϩ49-221-470-5057; e-mail: thomas.ziegler@uni-koeln.de
0040–4020/00/$ - see front matter ᭧ 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(99)01053-4

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G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
Scheme 2. (i) Ac2O, pyridine, 87% 2, 86% 5; (ii) NaCNBH3, HCl in Et2O, 82%; (iii) NIS, cat. TMSOTf, Ϫ30ЊC, MeCN, 21% 6a, 3% 6b.
influence this selectivity we first prepared the disaccharides
6 by a classical approach as follows (Scheme 2). Benzyl
2-O-benzoyl-4,6-O-benzylidene-a-d-glucopyranoside10 (1)
was conventionally acetylated to give 2, the benzylidene
acetal of which was regioselectively opened11 to afford
acceptor 3. Next, phenyl 1-thio-mannoside donor 5 was
prepared via intermediate 4 from phenyl 1-thio-a-d-manno-
pyranoside12 by sequential tritylation (Trt-Cl, pyridine),
benzylation (BnBr, NaH, DMF), detritylation (aqueous
HCl, acetone), and acetylation (Ac2O, pyridine). Coupling
of 3 and 5 under activation with N-iodosuccinimide (NIS)
and a catalytic amount of trimethylsilyl trifluoromethane-
sulfonate (TMSOTf) then afforded disaccharides 6 in 24%
overall yield. Compound 6 was formed as a 88:12 mixture
of the anomers 6a and 6b, respectively.
Next, for the systematic variation of the tethers and of the
activation procedures for intramolecular mannosylations a
series of differently linked prearranged glycosides 13, 16,
and 17 were prepared (Schemes 3 and 4). Starting from
known ethyl 2,3,4-tri-O-benzyl-1-thio-a-d-mannopyrano-
side13 (7), esterification with t-butyl malonate14 and dicyclo-
hexyl carbodiimide (DCC) afforded compound 8, the t-butyl
group of which was hydrolyzed with CF3CO2H to give
mannoside 9. Similarly, 7 was treated with succinic
anhydride as previously described8,9,10b,11a to afford the
succinate 10. Acids 9 and 10 were condensed with benzyl-
idene protected glucosides 1 and 11,15 respectively, and the
intermediates 12a–c were finally converted into the pre-
arranged glycosides 13a–c (Scheme 3). In the case of
compounds 12a,b and 13a,b, respectively, the condensation
Scheme 3. (i) HO2C–CH2–CO2t-Bu, DCC (64%); (ii) CF3CO2H (100%); (iii) succinic anhydride, pyridine, cat. DMAP (85%); (iv) (a,b) 1, DCC, cat. DMAP;
(c) 11, 2-chloro-1-methyl pyridiniumiodide, (n-Bu)33N; (v) (a,b) NaCNBH3, HCl in Et2O; (c) Et3SiH, CF3CO2H.

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
565
Scheme 4. (i) (a) COCl2, pyridine; (b) (CO)2Cl2, pyridine; (c) HO2C–CH2–CO2t-Bu, DCC; (d) succinic anhydride, pyridine, cat. DMAP; (e) phthaloyl
dichloride, pyridine or phthalic anhydride, pyridine, cat. DMAP; (ii) CF3CO2H; (iii) (a) 1, pyridine; (b) 1, DCC, cat. DMAP; (iv) NaCNBH3, HCl in Et2O; (v)
m-chloroperbenzoic acid.
and reductive ring opening of the benzylidene group could
be performed conventionally as described above. However,
the condensation of 9 and 11 with DCC as well as reduction
of the benzylidene group of 12c with NaCNBH3 proceeded
sluggishly and gave 13c in poor yield. A similar observation
has been previously made.15 Therefore, Mukaiyama’s
method (2-chloro-1-methyl pyridiniumiodide, tri-n-butyl-
amine)16 was applied for the condensation step and
DeNinno’s method (Et3SiH, CF3CO2H)17 for the regio-
selective benzylidene ring opening which both gave
satisfactory yields.
In similar sequences, phenyl 2,3,4-tri-O-benzyl-1-thio-a-d-
mannopyranoside (4) was used for the introduction of
different tethers as outlined in Scheme 4. Treatment of 4
with phosgene and oxallylchloride in pyridine, respectively,
afforded compounds 14a and 14b, which were both used
without further purification. Esterification of the latter
with glucoside 1 then gave first intermediates 15a and
15b, which were once again converted into the prearranged
glycosides 16a and 16b by reduction with NaCNBH3.
Furthermore, the corresponding sulfoxides 17a and 17b
were prepared as well according to Kahne’s procedure18
Scheme 5. (i) For activation, R1, R2, and X see Table 1; (ii) (1) cat. NaOMe in MeOH; (2) BzCl, pyridine.

566
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
Table 1. Intramolecular glycosylation of compounds 13, 16, and 17
Entry
Starting material
R1
SEt
R2
X
Ring size
12
Activationa
Solvent
Yield (%) 18
Yield (%) 19
Ratio a:b
1
2
3
4
5
6
7
8
13a
OBz
Malonate
A
A
B
B
A
A
B
B
C
C
A
A
B
B
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
13 18a
17 18a
6 18a
9 18a
38 18b
43 18b
27 18b
31 18b
36 18b
40 18b
0 18c
0 18c
0 18c
0 18c
–
58 19a
53 19a
73 19a
68 19a
33 19b
27 19b
43 19b
37 19b
37 19b
32 19b
51 19c
47 19c
52 19c
49 19c
–
18:82
24:76
8:92
12:88
53:47
61:39
39:61
46:54
49:51
56:44
0:100
0:100
0:100
0:100
13b
SEt
OBz
Succinate
13
9
10
11
12
13
14
15
13c
16a
SEt
NPhth
OBz
Malonate
Carbonate
12
10
b
SPh
A, D, E
–
c
16
C, B
–
–
–
17
18
19
17a
16b
SOPh
SPh
OBz
OBz
Carbonate
Oxalate
10
11
F
F
76 18d
79 18d
–
0 19d
0 19d
–
100:0
100:0
b
A, B, D, E
–
c
20
C
–
–
–
21
22
23
24
25
26
27
28
29
30
17b
16c
16d
17c
16e
SOPh
SPh
OBz
OBz
OBz
OBz
OBz
Oxalate
11
12
13
13
13
F
F
72 18e
75 18e
22 18a
25 18a
45 18b
53 18b
48 18b
54 18b
69 18f
63 18f
0 19e
0 19e
100:0
100:0
29:71
33:67
64:36
72:28
67:33
70:30
89:11
86:14
Malonate
Succinate
Succinate
Phthalate
A
A
A
A
F
F
A
A
54 19a
50 19a
25 19b
21 19b
23 19b
23 19b
9 19f
SPh
SOPh
SPh
10 19f
a A: NIS, cat TMSOTf, Ϫ30ЊC; B: MeOTf, 20ЊC; C: IDCP, 20ЊC; D: DMTST, 20ЊC; E: Br2, AgOTf, 25ЊC; F: Tf2O, 2,6-di-t-butyl-pyridine, Ϫ50 to 20ЊC.
b Decomposition.
c No reaction.
(m-chloroperbenzoic acid). The malonyl tether was intro-
duced via 14c and 15c as described above. Similarly,
succinates 14d, 15d, 16d, and 17c were obtained accord-
ingly and as described previously.8 For the synthesis of the
phthaloyl tethered glycosides, two approaches have been
tested. First, 4 was condensed with phthalicdichloride to
give crude 14e. However, all attempts to esterify the latter
with glucoside 1 failed. Therefore, 4 was treated with
phthalic anhydride to give the acid 14e0 the condensation
of which with 1 and DCC proceeded without any problems
and afforded 15e in 70% yield. Finally, ring opening of the
benzylidene acetal of the latter with NaCNBH3 gave
prearranged glycoside 16e.
residues of all individual compounds. Typically, coupling
constants of 153–160 Hz are indicative for b-linked
mannose residues and constants of 162–173 Hz are
indicative for a-linked mannosides.25 For a-linked
disaccharides 18, the coupling constants were found to be
in the range 164.3–168.5 Hz, and for b-linked disaccharides
19 in the range 153.1–153.4 Hz. Furthermore, deacylation
of tethered compounds 18 and 19 followed by rebenzoyl-
ation of the intermediates afforded disaccharides 20 and 21
(Scheme 5) which also showed significant coupling
constants of 171.8, 156.8, and 154.8 Hz, respectively.
In general, the following global properties of intramolecular
glycosylations could be deduced from the experiments. (1)
All intramolecular glycosylations (except those performed
on carbonate and oxalate tethered 1-thio-glycosides 16a and
16b with procedures A–E, cf. Table 1, entries 15 and 19)
proceeded with significantly higher yield than the inter-
molecular mannosylation between 3 and 5 (Scheme 2).
Particularly, under identical conditions (activation with
NIS), intramolecular mannosylations (Table 1, entries 1,
5, 23, 25, and 29) gave a 70–80% yield of the corresponding
disccharides 18 and 19 whereas the intermolecular
mannosylation afforded disaccharides 6 in poor 24%
yield. Similar observations have been previously made for
intramolecular (1!4)-selective rhamnosylations of galacto-
sides.26 (2) Except for intramolecular mannosylations with
All prearranged glycosides 13, 16, and 17 were used for
intramolecular mannosylations (Scheme 5) using NIS and
a catalytic amount of TMSOTf at Ϫ30ЊC (procedure A),19
methyl trifluoromethanesulfonate (MeOTf) at 20ЊC (pro-
cedure B),20 iodoniumdicollidine perchlorate (IDCP) at
20ЊC (procedure C),21 dimethyl methylthiosulfoniumtriflate
(DMTST) at 20ЊC (procedure D),20a,22 Br2 and silver
trifluoromethanesulfonate (AgOTf) at 20ЊC (procedure
E),23 and trifluoromethanesulfonic anhydride (Tf2O) at
Ϫ50 to 20ЊC (procedure F).24 The results are summarized
in Table 1. The anomeric configurations of the obtained
1
disaccharides were determined by measuring the JC-1,1-H
-
coupling constants at the anomeric centers of the mannose

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
567
Scheme 6. (i) Succinic anhydride, pyridine, cat. DMAP, 82%; (ii) 1, DCC, cat. DMAP, 73%; (iii) NaCNBH3, HCl in Et2O, 93%; (iv) (a) NIS, cat. TMSOTf,
MeCN, 63%; (b) NIS, cat. TMSOTf, CH2Cl2, 70%; (v) (1) cat. NaOMe in MeOH; (2) BzCl, pyridine, 81%.
phthalate tethered prearranged glycoside 16e (entry 29)
which resulted in an anomeric mixture of a:bˆ89:11, all
other glycosylations proceeded with significantly higher
b-content (up to a:bˆ8:92 in entry 3) than the inter-
molecular mannosylation of 3 and 5 which gave an a:b
mixture of 88:12 (Scheme 2). (3) There was no strong
solvent dependence of the diastereoselectivity as was
previously observed for other intramolecular glycosyl-
ations.27 (4) No dramatic change in diastereoselectivity
could be observed for different activation procedures (cf.
entries 1–4 vs. 23 and 24, 5–10 vs. 25–28). In contrast, a
complete inversion of the anomeric selectivity has been
found for intramolecular condensations with succinate
tethers at position 3 of the mannosyl donor.8 (5) Highest
yields of b-(1!4)-linked products were obtained when a
12-membered ring was formed with malonate tethered
compounds 13a (entries 3 and 4) and 13c (entries 11–14).
using a Monte-Carlo conformation search with the
AMBER force field implemented in MacroModel29 showed
the a-linked products 18b, 18d, 18e, and 18f to be 26.6–
55.5 kJ/mol more stable than the corresponding b-linked
disaccharides. Solely, for malonate tethered disaccharides
the b-linked products 19b and 19c were ca. 4 kJ/mol more
stable than the a-linked counterpart. However, additional
factors like the activation procedure used for the ring
closure and the blocking groups at the mannosyl donor
play also a significant role for the anomeric outcome. The
latter influence was previously encountered for other
intramolecular glycosylations9,11a,26–28 and was also
demonstrated here for prearranged glycoside 25 which had
neighboring active benzoyl groups instead of benzyl groups
as in compounds 13b, 16d, and 17c.
Compound 25 was prepared as outlined above by succinoyl-
ation of 2212 to give first succinate 23, condensation of
which with 1 then afforded 24, and reductive ring opening
of the latter finally gave 25 (Scheme 6). When glycoside 25
was treated with NIS under identical conditions as in
Table 1, solely the a-linked disaccharide 26 was obtained
in 70% yield whereas the corresponding benzyl protected
glycoside 16d afforded a 72:28 a/b-mixture in 74% yield
(Table 1, entry 26). Once again, the a-linkage in 26 was
unambiguously assigned by the found CH-coupling
constant of 168.2 Hz and by converting 26 into 27 which
also had JC-1,1-Hˆ167.5 Hz.
Obviously, a strong influence of the tether on the diastereo-
selectivity of intramolecular mannosylations is operative.
When a 10-membered ring is formed (carbonate tethers,
entries 15–18) solely activation of the sulfoxide 17a gave
a-linked product 18d. No b-linked product 19d was found
in this case. Similarly, for an 11-membered ring (oxalate
tether, entries 19–22) 17b resulted in exclusive formation
of the corresponding a-linked disaccharide 18e. No reaction
or decomposition of the starting materials 16a, and 16b,
respectively, was observed for other activation procedures.
The formation of 12-membered rings (i.e. a malonate tether,
entries 1–4, 11–14, 23, and 24) resulted in high contents of
the b-linked products 19a and 19c, respectively, whereas
the formation of 13-membered rings (i.e. succinate and
phthalate tethers, entries 5–10, 25–30) gave again
higher contents of a-linked disaccharides 18b and 18f,
respectively.
Experimental
General
The NMR data were obtained from spectra measured in
CDCl3 solutions (with Me4Si as internal standard) at 25ЊC
with Bruker AC 300F and DRX 500 spectrometers at 300
and 500 MHz for 1H NMR spectra, and 75 and 126 MHz for
13C NMR spectra, respectively. 1H NMR signal assignments
were made by first-order analysis of the spectra and by
HH-COSY spectra. Of the two magnetically non-equivalent
geminal protons at C-6, the one resonating at lower field was
The influence of the tether on the anomeric selectivity of
intramolecular mannosylations can be put down at least in
part to the differences in the thermodynamic stability of the
disaccharides 18 and 19. A similar observation has been
made previously for intramolecular galactosylations.28
Molecular modeling studies for compounds 18 and 19

568
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
allocated 6a-H and the one resonating at higher field 6b-H.
13C NMR assignments were made by mutual comparison of
the spectra, by DEPT spectra, and by CH-COSY spectra.
Optical rotations were measured at 25ЊC with a Perkin–
Elmer automatic polarimeter, Model 241. TLC was
performed on precoated plastic sheets, Polygram SIL
UV254, 40×80 mm (Macherey–Nagel) using appropriately
adjusted mixtures of toluene/ethyl acetate. Detection was
effected by UV light, where applicable, and by charring
with 5% H2SO4 in ethanol. CC was performed by eluting
from columns of Silica Gel 60 (Merck) with appropriately
adjusted mixtures of toluene/ethyl acetate. Solutions in
organic solvents were dried with anhydrous Na2SO4 and
concentrated at 2 kPa, Ͻ40ЊC.
(4.81 g, 17.7 mmol) and tritylchloride (4.56 g, 16.4 mmol)
in pyridine (20 ml) was stirred at 20ЊC for 24 h. The mixture
was poured into water and extracted with dichloromethane.
The extracts were washed with water, dried and concen-
trated to give crude phenyl 6-O-trityl-1-thio-a-d-manno-
pyranoside (7.65 g). BnBr (5.27 ml, 44.6 mmol) was
added at 0ЊC to a solution of the crude tritylated inter-
mediate and NaH (2.06 g, 85.8 mmol) in DMF (30 ml)
and the mixture was stirred at 20ЊC for 3 h. Excess NaH
was destroyed by careful addition of MeOH and the mixture
was poured into water and extracted with dichloromethane.
The extracts were washed with aqueous NaHCO3 solution,
dried and concentrated. Chromatography (CCl4/acetone 5:1)
of the residue afforded phenyl 2,3,4-tri-O-benzyl-6-O-trityl-
1-thio-a-d-mannopyranoside (9.0 g, 70%), [a]Dˆϩ80.1
(cˆ1.1, CHCl3). 1H NMR (significant signal, CDCl3):
dˆ5.70 (d, 1H, J1,2ˆ1.4 Hz, 1-H). 13C NMR (CDCl3):
dˆ85.3 (C-1), 80.2 (C-3), 77.1 (C-4), 75.2 (C-2), 72.8
(C-5), 62.8 (C-8). Anal. calcd for C52H48O5S: C, 79.56; H,
6.16; S, 4.09; Found: C, 79.39; H, 6.21; S, 3.85.
Benzyl 3-O-acetyl-2-O-benzoyl-4,6-O-benzylidene-a-d-
glucopyranoside (2). A solution of benzyl 2-O-benzoyl-
4,6-O-benzylidene-a-d-glucopyranoside10 (1, 1.16 g, 2.51
mmol) and acetic anhydride (1.42 ml, 15.06 mmol) in
pyridine (15 ml) was stirred at 20ЊC for 24 h, poured into
water and extracted with dichloromethane. The organic
extracts were washed with aqueous HCl solution, dried
and concentrated. Chromatography (n-hexane/ethyl acetate
5:1) of the residue afforded 2 (1.10 g, 87%), [a]Dˆϩ134.8
(cˆ0.9, CHCl3). 1H NMR (CDCl3): dˆ5.85 (t, 1H,
J3,4ˆ9.9 Hz, 3-H), 5.53 (s, 1H, PhCH), 5.27 (d, 1H,
J1,2ˆ4.1 Hz, 1-H), 5.07 (dd, 1H, J2,3ˆ10.0 Hz, 2-H), 4.75
(d, 1H, JˆϪ12.4 Hz, PhCH2), 4.54 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.26 (dd, 1H, J5,6aˆ4.9 Hz, J6a,6bˆϪ10.1 Hz,
6a-H), 4.08 (dt, 1H, J5,6bˆ10.2 Hz, 5-H), 3.79 (t, 1H,
6b-H), 1.99 (s, 3H, COCH3). 13C NMR (CDCl3):
dˆ169.9, 165.7 (CO), 101.6 (PhCH), 95.9 (C-1), 79.2
(C-4), 72.3 (C-2), 69.9 (PhCH2), 68.9 (C-3), 68.3 (C-6),
62.8 (C-5), 20.8 (COCH3). Anal. calcd for C29H28O8: C,
69.04; H, 5.59; Found: C, 69.00; H, 5.66.
(b) A solution of phenyl 2,3,4-tri-O-benzyl-6-O-trityl-1-
thio-a-d-mannopyranoside (5.95 g, 7.6 mmol) and 1 M
aqueous HCl solution (15 ml) in acetone (150 ml) was stir-
red at 60ЊC for 24 h. The mixture was cooled to 20ЊC,
washed with aqueous NaHCO3 solution, dried and concen-
trated. Chromatography (CCl4/acetone 15:1) of the residue
afforded 4 (2.51 g, 61%), [a]Dˆϩ86.1 (cˆ1.0, CHCl3). 1H
NMR (CDCl3): dˆ5.51 (d, 1H, J1,2ˆ1.6 Hz, 1-H), 4.69 (d,
1H, PhCH2), 4.67 (s, 2H, PhCH2), 4.65 (d, 1H, PhCH2), 4.61
(d, 1H, PhCH2), 4.60 (d, 1H, PhCH2), 4.15–4.09 (m, 1H,
5-H), 4.05 (t, 1H, J3,4ˆJ4,5ˆ9.5 Hz, 4-H), 3.99 (dd, 1H,
J2,3ˆ3.1 Hz, 2-H), 3.88 (dd, 1H, 3-H), 3.81–3.75 (m, 2H,
6a-H, 6b-H). 13C NMR (CDCl3): dˆ86.0 (C-1), 80.3 (C-3),
76.4 (C-4), 75.3 (PhCH2), 74.7 (C-2), 73.2 (C-5), 72.3, 72.2
(PhCH2), 62.2 (C-6). Anal. calcd for C33H34O5S: C, 73.04;
H, 6.31; S, 5.91; Found: C, 72.82; H, 6.28; S, 5.74.
Benzyl 3-O-acetyl-2-O-benzoyl-6-O-benzyl-a-d-glucopy-
ranoside (3). A solution of HCl in Et2O was added
portionwise at 20ЊC to a stirred suspension of 2 (0.93 g,
Phenyl 6-O-acetyl-2,3,4-tri-O-benzyl-1-thio-a-d-manno-
pyranoside (5). Treatment of 4 (3.07 g, 5.7 mmol) with
acetic anhydride (3.2 ml, 34 mmol) in pyridine (30 ml) as
described for compound 2 afforded 5 (2.84 g, 86%),
˚
1.84 mmol), 3 A molecular sieves (ca. 0.5 g) and NaCNBH3
(1.45 g, 23 mmol) in THF (15 ml) until the evolution of gas
ceased. The mixture was diluted with dichloromethane and
filtered through a layer of Celite. The filtrate was washed
with aqueous NaHCO3 solution and water, dried and
concentrated. Chromatography (CCl4/acetone 6:1) of the
residue afforded 3 (0.77 g, 82%), [a]Dˆϩ118.1 (cˆ1.1,
1
[a]Dˆϩ75.8 (cˆ2.0, CHCl3). H NMR (CDCl3): dˆ5.57
(d, 1H, J1,2ˆ1.6 Hz, 1-H), 4.95 (d, 1H, JˆϪ10.8 Hz,
PhCH2), 4.72 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.63 (d, 1H,
JˆϪ10.8 Hz, PhCH2), 4.61–4.57 (m, 3H, PhCH2), 4.35–
4.29 (m, 3H, J5,6aˆ4.6 Hz, 5-H, 6a-H, 6b-H), 4.00 (dd,
1H, J2,3ˆ2.9 Hz, 2-H), 3.97–3.93 (m, 1H, 4-H), 3.88 (dd,
1H, J3,4ˆ9.2 Hz, 3-H), 2.01 (s, 3H, COCH3). 13C NMR
(CDCl3): dˆ170.8 (COCH3), 85.5 (C-1), 80.1 (C-3), 76.0
(C-2), 75.3 (PhCH2), 74.6 (C-4), 72.1, 71.9 (PhCH2), 70.9
(C-5), 63.5 (C-6), 20.8 (COCH3). Anal. calcd for
C35H36O6S: C, 71.89; H, 6.20; S, 5.48; Found: C, 72.00;
H, 6.25; S, 5.40.
1
CHCl3). H NMR (CDCl3): dˆ5.59 (dd, 1H, J3,4ˆ9.1 Hz,
3-H), 5.23 (d, 1H, J1,2ˆ3.7 Hz, 1-H), 5.04 (dd, 1H,
J2,3ˆ10.2 Hz, 2-H), 4.73 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.63 (d, 1H, JˆϪ12.0 Hz, PhCH2), 4.57 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.52 (d, 1H, JˆϪ12.4 Hz, PhCH2),
3.97–3.91 (m, 1H, J5,6aˆ4.2 Hz, J5,6bˆ4.0 Hz, 5-H), 3.88–
3.84 (m, 1H, J4,5ˆ9.5 Hz, 4-H), 3.78 (dd, 1H,
J6a,6bˆϪ10.4 Hz, 6a-H), 3.70 (dd, 1H, 6b-H), 2.88 (d, 1H,
J4,OHˆ3.8 Hz, OH), 2.02 (s, 2H, COCH3). 13C NMR
(CDCl3): dˆ171.5 (COCH3), 165.7 (PhCO), 95.2 (C-1),
73.4 (PhCH2), 73.0 (C-3), 71.4 (C-2), 70.5 (C-5), 70.3
(C-4), 69.7 (PhCH2), 69.5 (C-6), 20.9 (COCH3). Anal.
calcd for C29H30O8: C, 68.76; H, 5.97; Found: C, 68.96; H
6.10.
Benzyl O-(6-O-acetyl-2,3,4-tri-O-benzyl-a-d-mannopyr-
anosyl)-(1!4)-3-O-acetyl-2-O-benzoyl-6-O-benzyl-a-d-
glucopyranoside (6a) and benzyl O-(6-O-acetyl-2,3,4-tri-
O-benzyl-b-d-mannopyranosyl)-(1!4)-3-O-acetyl-2-O-
benzoyl-6-O-benzyl-a-d-glucopyranoside (6b). A mixture
of 3 (0.67 g, 1.32 mmol), 5 (0.92 g, 1.58 mmol), NIS
˚
Phenyl 2,3,4-tri-O-benzyl-1-thio-a-d-mannopyranoside (4).
(a) A solution of phenyl 1-thio-a-d-mannopyranoside12
(1.50 g, 6.6 mmol) and 4 A molecular sieves (ca. 0.5 g) in
MeCN (20 ml) was cooled under Ar to Ϫ30ЊC. TMSOTf

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
569
(61 ml, 0.33 mmol) was added with a syringe, the mixture
was stirred for 10 min, neutralized by addition of pyridine,
diluted with dichloromethane and filtered. The filtrate was
washed with aqueous NaHCO3 and Na2S2O3 solution, dried
and concentrated. Chromatography (toluene/acetone 25:1)
of the residue afforded first 6a (278 mg, 21%), [a]Dˆϩ84.8
(cˆ1.0, CHCl3). 1H NMR (CDCl3): dˆ5.61 (t, 1H,
J3,4ˆ8.9 Hz, 3-H), 5.22 (d, 1H, J1,2ˆ3.6 Hz, 1-H), 5.08 (s,
1H, 10-H), 4.95 (dd, 1H, J2,3ˆ10.3 Hz, 2-H), 4.86 (d, 1H,
JˆϪ10.9 Hz, PhCH2), 4.72 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.66–4.59 (m, 6H, PhCH2), 4.64 (d, 1H, JˆϪ11.7 Hz,
PhCH2), 4.56 (d, 1H, JˆϪ12.7 Hz, PhCH2), 4.22 (bs, 2H,
6a0-H, 6b0-H), 3.98–3.79 (m, 6H, 30-H, 40-H, 4-H, 50-H,
5-H, 6a-H), 3.71–3.67 (m, 2H, 20-H, 6b-H), 1.98 (s, 3H,
COCH3), 1.73 (s, 3H, COCH3). 13C NMR (CDCl3):
dˆ170.7, 169.9 (COCH3), 165.6 (PhCO), 100.0 (C-10,
J2,3ˆ3.2 Hz, J3,4ˆ10.1 Hz, 2-H, 3-H), 3.29 (s, 2H,
COCH2), 2.66–2.47 (m, 2H, SCH2CH3), 1.44 (s, 9H,
C(CH3)3), 1.23 (t, 3H, Jˆ7.4 Hz, SCH2CH3). 13C NMR
(CDCl3): dˆ166.9 (CO), 165.4 (CO), 82.0 (C(CH3)3),
81.9 (C-1), 80.2 (C-3), 76.2 (C-2), 75.2 (PhCH2), 74.6
(C-4), 72.0 (2 C, PhCH2), 70.1 (C-5), 64.3 (C-6), 42.6
(COCH2), 27.9 (C(CH3)3), 25.4 (SCH2CH3), 14.9
(SCH2CH3). Anal. calcd for C36H44O8S: C, 67.90; H, 6.96;
S, 5.04; Found: C, 67.94; H, 7.08; S, 5.11.
Ethyl 2,3,4-tri-O-benzyl-6-O-(hydroxycarbonylethanoyl)-
1-thio-a-d-mannopyranoside (9). Trifluoroacetic acid
(5.3 ml, 51.8 mmol) was added at room temperature to a
solution of 8 (1.65 g, 2.59 mmol) in dichloromethane
(80 ml), the mixture was stirred for 3 h and concentrated.
Coevaporation of toluene (three times) afforded crude 9
(2.58 g, 100%) which was used without further purification
in the next step.
JC-1 ,1 -Hˆ170.3 Hz), 94.9 (C-1), 79.6 (C-30), 76.1, 74.2
(C-4,40), 74.9 (2 C, C-20, PhCH2), 73.4 (PhCH2), 72.4
(PhCH2), 72.3 (C-3), 72.1 (PhCH2), 71.8 (C-2), 71.3
(C-5), 70.1 (C-50), 69.8 (PhCH2), 68.5 (C-6), 63.6
(C-60), 20.8 (2 C, COCH3). Anal. calcd for C58H60O14:
C, 71.01; H, 6.16; Found: C, 70.89; H, 6.09.
0
0
Ethyl 2,3,4-tri-O-benzyl-6-O-(3-hydroxycarbonylpropa-
noyl)-1-thio-a-d-mannopyranoside (10). A solution of
713 (2.33 g, 4.71 mmol), succinic anhydride (3.8 g,
37.7 mmol) and a catalytic amount of DMAP (ca. 0.1 g)
in pyridine (50 ml) was stirred at 20ЊC for 24 h and concen-
trated. The residue was dissolved in dichloromethane,
washed with aqueous HCl and NaHCO3 solution and
water, dried and concentrated to give crude 10 (2.36 g,
85%) which was used without further purification in the
next step.
Eluted next was 6b (44.4 mg, 3%), [a]Dˆϩ45.0 (cˆ1.3,
1
CHCl3). H NMR (CDCl3): dˆ5.76 (t, 1H, J3,4ˆ9.8 Hz,
3-H), 5.28 (d, 1H, J1,2ˆ3.8 Hz, 1-H), 5.02 (dd, 1H,
J2,3ˆ10.3 Hz, 2-H), 4.91 (d, 1H, JˆϪ10.9 Hz, PhCH2),
4.84 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.73 (d, 1H,
JˆϪ12.4 Hz, PhCH2), 4.65 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.64 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.57 (d, 1H,
JˆϪ12.9 Hz, PhCH2), 4.55 (d, 1H, JˆϪ12.5 Hz, PhCH2),
4.51 (bs, 1H, PhCH2), 4.42 (d, 1H, JˆϪ11.9 Hz, PhCH2),
4.40 (d, 1H, JˆϪ12.1 Hz, PhCH2), 4.33 (s, 1H, 10-H), 4.28
Ethyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-carbo-
nylethanoyl]-1-thio-a-d-mannopyranoside (12a). Treat-
ment of crude 9 (1.29 g, 2.2 mmol) and 110 (1.13 g,
2.44 mmol) with DCC (0.5 g, 2.44 mmol) and a catalytic
amount of DMAP in dichloromethane (40 ml) at 20ЊC for
24 h as described for the preparation of 8 and chromato-
graphy (toluene/acetone 10:1) afforded 12a (1.67 g, 67%),
(bd, 2H, 6a0-H, 6b0-H), 4.01 (t, 1H, J4,5ˆ9.7 Hz, 4-H), 3.92–
0
0
0
3.89 (m, 1H, 5-H), 3.78 (t, 1H, J4 ,5 ˆ9.4 Hz, 4 -H), 3.65
0
0
0
(bd, J2 ,3 ˆ2.9 Hz, 2 -H), 3.58 (bd, 2H, 6a-H, 6b-H), 3.33–
0
3.30 (m, 1H, 50-H), 3.29 (dd, 1H, J3 ,4 ˆ9.3 Hz, 3 -H), 2.00
(s, 3H, COCH3), 1.95 (s, 3H, COCH3). 13C NMR (CDCl3):
dˆ170.8, 170.4 (COCH3), 165.7 (PhCO), 100.9 (C-10,
0
0
1
[a]Dˆϩ101.4 (cˆ1.6, CHCl3). H NMR (CDCl3): dˆ5.87
JC-1 ,1 -Hˆ152.2 Hz), 95.3 (C-1), 82.2 (C-30), 75.0 (PhCH2),
74.9 (C-4), 74.3 (C-40), 73.8 (C-20), 73.6 (1 C, 2 C, C-50,
PhCH2), 71.8 (C-2), 71.3 (PhCH2), 70.1 (C-5), 69.8
(PhCH2), 69.7 (C-3), 68.1 (C-6), 63.6 (C-60), 20.8, 20.7
(COCH3). Anal. calcd for C58H60O14: C, 71.01; H, 6.16;
Found: C, 71.20; H, 6.10.
(t, 1H, J3,4ˆ9.9 Hz, 3-H), 5.49 (s, 1H, PhCH), 5.30 (d, 1H,
0
0
0
0
0
J1,2ˆ3.8 Hz, 1-H), 5.28 (d, 1H, J1 ,2 Ͻ1.0 Hz, 1 -H), 5.05
(dd, 1H, J2,3ˆ9.9 Hz, 2-H), 4.86 (d, 1H, JˆϪ10.8 Hz,
PhCH2), 4.74 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.68 (d, 1H,
JˆϪ12.4 Hz, PhCH2), 4.61 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.55–4.53 (m, 3H, PhCH2), 4.50 (d, 1H, JˆϪ10.8 Hz,
PhCH2), 4.25 (dd, 1H, J5,6aˆ5.0 Hz, J6a,6bˆϪ10.4 Hz,
6a-H), 4.22–4.19 (m, 2H, 6a0-H, 6b0-H), 4.16–4.02 (m,
2H, 5-H, 50-H), 3.83–03.68 (m, 3H, 20-H, 4-H, 6b-H), 3.71
Ethyl 2,3,4-tri-O-benzyl-6-O-(t-butyloxycarbonylethano-
yl)-1-thio-a-d-mannopyranoside (8). DCC (0.96 g, 4.65
mmol) was added at 0ЊC to a solution of 713 (2.09 g,
4.23 mmol), t-butyl malonate14 (0.75 g, 4.65 mmol) and 1-
hydroxy-1H-benzotriazole (0.69 g, 5.08 mmol) in dichloro-
methane (30 ml). The mixture was stirred at 20ЊC for 24 h,
diluted with dichloromethane and filtered through a layer of
Celite. The filtrate was subsequently washed with aqueous
HCl and NaHCO3 solution, dried and concentrated. Chro-
matography (n-hexane/ethyl acetate 6:1) of the residue
afforded 8 (1.73 g, 64%), [a]Dˆϩ58.0 (cˆ1.1, CHCl3).
1H NMR (CDCl3): dˆ5.33 (d, 1H, J1,2ˆ1.0 Hz, 1-H), 4.92
(d, 1H, JˆϪ10.7 Hz, PhCH2), 4.71 (d, 1H, JˆϪ12.5 Hz,
PhCH2), 4.65 (d, 1H, JˆϪ12.5 Hz, PhCH2), 4.60–4.56 (m,
3H, PhCH2), 4.44 (dd, 1H, J5,6aˆ5.1 Hz, J6a,6bˆϪ11.8 Hz,
6a-H), 4.36 (dd, 1H, J5,6bˆ2.2 Hz, 6b-H), 4.18 (ddd, 1H,
5-H), 3.93 (t, 1H, J4,5ˆ9.4 Hz, 4-H), 3.83 (2 dd, 2H,
0
0
(t, 1H, J4 ,5 ˆ9.7 Hz, 4 -H), 3.32 (s, 2H, COCH2), 2.56–2.41
(m, 2H, SCH2CH3), 1.17 (t, 3H, Jˆ7.4 Hz, SCH2CH3). 13C
NMR (CDCl3): dˆ165.8 (CO), 165.6 (CO), 165.3 (CO),
101.5 (PhCH), 95.8 (C-1), 81.8 (C-10), 80.2 (C-30), 78.9
(C-4), 76.0 (C-20), 75.0 (PhCH2), 74.6 (C-40), 72.2 (C-2),
72.0 (2 C, PhCH2), 70.0 (2 C, C-3, C-50), 69.9 (PhCH2), 68.8
(C-6), 62.8 (C-5), 64.3 (C-60), 41.1 (COCH2), 25.3
(SCH2CH3), 14.9 (SCH2CH3). Anal. calcd for C59H60O14S:
C, 69.12; H, 5.90; S, 3.13; Found: C, 68.82; H, 5.92; S, 3.14.
Ethyl 2,3,4-tri-O-benzyl-6-O-[3-(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-carbonyl-
propanoyl]-1-thio-a-d-mannopyranoside (12b). Treat-
ment of crude 10 (1.58 g, 2.7 mmol) and 110 (1.23 g,
2.7 mmol) with DCC (0.61 g, 3.0 mmol) and a catalytic

570
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
amount of DMAP in dichloromethane (15 ml) at 20ЊC for
30 h as described for the preparation of 8 and chromato-
graphy (toluene/ethyl acetate 8:1) afforded 12b (1.85 g,
67%), [a]Dˆϩ103.1 (cˆ1.1, CHCl3). H NMR (CDCl3):
1H NMR (CDCl3): dˆ5.67 (dd, 1H, J3,4ˆ9.1 Hz, 3-H), 5.30
(s, 1H, 10-H), 5.25 (d, 1H, J1,2ˆ3.7 Hz, 1-H), 4.97 (dd, 1H,
J2,3ˆ10.3 Hz, 2-H), 4.90 (d, 1H, JˆϪ11.0 Hz, PhCH2), 4.74
(d, 1H, JˆϪ12.4 Hz, PhCH2), 4.68 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.61–4.58 (m, 2H, PhCH2), 4.55 (s, 3H, PhCH2),
4.54 (d, 1H, JˆϪ11.0 Hz, PhCH2), 4.52 (d, 1H,
1
dˆ5.88 (t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.52 (s, 1H, PhCH),
5.33 (s, 1H, 10-H), 5.29 (d, 1H, J1,2ˆ3.8 Hz, 1-H), 5.08
(dd, 1H, J2,3ˆ10.0 Hz, 2-H), 4.90 (d, 1H, JˆϪ10.9 Hz,
PhCH2), 4.76 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.69–4.57
(m, 4H, PhCH2), 4.55 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.53
(d, 1H, JˆϪ10.9 Hz, PhCH2), 4.27 (dd, 1H,
J6a,6bˆϪ10.1 Hz, 6a-H), 4.19–4.17 (m, 2H, 6a0-H, 6b0-H),
4.13–4.04 (m, 2H, J5,6aˆ4.9 Hz, 5-H, 50-H), 3.93–3.78 (m,
4H, 20-H, 30-H, 40-H, 6b-H), 3.74 (t, 1H, J4,5ˆ9.7 Hz, 4-H),
2.60–2.53 (m, 6H, CH2CH2, SCH2CH3), 1.21 (t, 3H,
Jˆ7.4 Hz, SCH2CH3). 13C NMR (CDCl3): dˆ171.6
(COCH2CH2), 171.1 (COCH2CH2), 165.7 (PhCO), 101.5
(PhCH), 95.9 (C-1), 81.9 (C-10), 80.3 (C-30), 79.1 (C-4),
76.1 (C-20), 75.1 (PhCH2), 74.5 (C-40), 72.2 (C-2), 72.0 (2
C, PhCH2), 69.9 (PhCH2), 69.2 (C-3), 68.8 (C-6), 63.5
(C-60), 62.8 (C-5), 29.0, 28.9 (COCH2CH2), 25.3
(SCH2CH3), 14.9 (SCH2CH3). Anal. calcd for C60H62O14S:
C, 69.35; H, 6.01; S, 3.09; Found: C, 69.29; H, 6.02; S, 3.07.
JˆϪ12.6 Hz, PhCH2), 4.37–4.30 (m, 2H, 6a0-H, 6b0-H),
0
0
0
4.13 (ddd, 1H, J5 ,6a ˆ2.6 Hz, 5 -H), 4.00–3.94 (m, 1H,
0
0
0
5-H), 3.92 (t, 1H, J4 ,5 ˆ9.6 Hz, 4 -H), 3.82–3.67 (m, 3H,
20-H, 30-H, 4-H), 3.54 (d, 1H, J4,OHˆ4.9 Hz, OH), 3.38 (d,
1H, JˆϪ16.1 Hz, COCH2), 3.30 (d, 1H, JˆϪ16.1 Hz,
COCH2), 2.54–2.47 (m, 2H, SCH2CH3), 1.19 (t, 3H,
Jˆ7.4 Hz, SCH2CH3). 13C NMR (CDCl3): dˆ167.1
(PhCO), 165.8 (CO), 165.7 (CO), 95.1 (C-1), 82.0 (C-10),
80.1 (C-30), 76.0, 74.5 (C-20,4), 75.1 (PhCH2), 74.1 (C-3),
73.6 (PhCH2), 71.9 (2 C, PhCH2), 71.4 (C-2), 70.7 (C-50),
69.8 (C-5), 69.5 (PhCH2), 69.2 (C-4), 69.0 (C-6), 64.6
(C-60), 41.4 (COCH2), 25.5 (SCH2CH3), 14.9 (SCH2CH3).
Anal. calcd for C59H62O14S: C, 68.99; H, 6.08; Found: C,
69.09; H, 6.02.
Ethyl 2,3,4-tri-O-benzyl-6-O-[3-(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-carbonylpropa-
noyl]-1-thio-a-d-mannopyranoside (13b). Treatment of
12b (2.11 g, 2.03 mmol) in THF (25 ml) with NaCNBH3
(1.59 g, 25.34 mmol) and HCl in Et2O as described for the
preparation of 3 and chromatography (toluene/ethyl acetate
3:1) afforded 13b (1.57 g, 74%), [a]Dˆϩ89.2 (cˆ1.5,
Ethyl 2,3,4-tri-O-benzyl-6-O-[(1-O-benzyl-4,6-O-benzyl-
idene-2-deoxy-2-phthalimido-a-d-glucopyranos-3-
yloxy)-carbonylethanoyl]-1-thio-a-d-mannopyranoside
(12c). A solution of crude 9 (1.26 g, 2.17 mmol), 1115 (0.9 g,
1.85 mmol) and n-Bu3N (1.1 ml, 4.44 mmol) in dichloro-
methane (15 ml) was added at 20ЊC under Ar to a suspen-
sion of 2-chloro-1-methyl-pyridiniumiodide (0.57 g,
2.22 mmol) in dichloromethane (5 ml). The mixture was
stirred for 2.5 h and concentrated. Chromatography (tolu-
ene/ethyl acetate 15:1) of the residue afforded 12c (1.55 g,
1
CHCl3). H NMR (CDCl3): dˆ5.66 (dd, 1H, J3,4ˆ9.2 Hz,
0
0
0
3-H), 5.34 (d, 1H, J1 ,2 ˆ1.0 Hz, 1 -H), 5.24 (d, 1H,
J1,2ˆ3.7 Hz, 1-H), 5.00 (dd, 1H, J2,3ˆ10.2 Hz, 2-H), 4.91
(d, 1H, JˆϪ10.9 Hz, PhCH2), 4.72 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.69 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.62 (d, 1H,
JˆϪ11.8 Hz, PhCH2), 4.57 (d, 1H, JˆϪ10.4 Hz, PhCH2),
4.56 (s, 3H, PhCH2), 4.53 (d, 1H, JˆϪ10.7 Hz, PhCH2),
4.52 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.28–4.22 (m, 2H,
1
80%), [a]Dˆϩ101.4 (cˆ1.1, CHCl3). H NMR (CDCl3):
dˆ6.80 (dd, 1H, J3,4ˆ9.4 Hz, 3-H), 5.50 (s, 1H, PhCH),
0
0
5.27 (d, 1H, J1 ,2 ˆ1.4 Hz, 1-H), 4.97 (d, 1H, J1,2ˆ3.8 Hz,
1-H), 4.83 (d, 1H, JˆϪ10.8 Hz, PhCH2), 4.72 (d, 1H,
JˆϪ12.6 Hz, PhCH2), 4.68 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.62 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.55 (dd, 1H, J2,3ˆ
11.2 Hz, 2-H), 4.53 (s, 2H, PhCH2), 4.45 (2 d, 2H, Jˆ
6a0-H, 6b0-H), 4.12 (ddd, 1H, J5 ,6a ˆ2.7 Hz, J5 ,6b
ˆ
0
0
0
0
2.7 Hz, 50-H), 3.99–3.93 (m, 1H, 5-H), 3.90 (t, 1H,
0
0
0
0
0
J4 ,5 ˆ9.4 Hz, 4 H), 3.83–3.77 (m, 3H, 2 -H, 3 -H, 4-H),
3.73 (dd, 1H, 6b-H), 3.30 (bs, 1H, OH), 2.70–2.43 (m,
6H, CH2CH2, SCH2CH3), 1.22 (t, 3H, Jˆ7.4 Hz,
SCH2CH3). 13C NMR (CDCl3): dˆ172.2 (2 C,
COCH2CH2), 165.7 (PhCO), 95.1 (C-1), 81.8 (C-10), 80.2
(C-30), 76.2, 74.4 (C-20,4), 75.1 (PhCH2), 73.6 (PhCH2),
73.4 (C-3), 72.0 (PhCH2), 71.9 (PhCH2), 71.5 (C-2), 70.5
(C-50), 70.1 (C-5), 69.7 (C-4), 69.5 (PhCH2), 69.2 (C-6),
63.7 (C-60), 29.2 (2 C, COCH2CH2), 25.4 (SCH2CH3),
15.0 (SCH2CH3). Anal. calcd for C60H64O14S: C, 69.21; H,
6.20; S, 3.08; Found: C, 69.38; H, 6.22; S, 3.29.
Ϫ10.6 Hz, JˆϪ12.7 Hz, PhCH2), 4.24 (dd, 1H, J5,6a
ˆ
5.0 Hz, J6a,6bˆϪ9.9 Hz, 6a-H), 4.16 (dt, 1H, J5,6bˆ9.9 Hz,
5-H), 4.09–3.99 (m, 3H, 50-H, 6a0-H, 6b00-H), 3.78 (dd, 1H,
0
0
0
0
J2 ,3 ˆ3.2 Hz, 2 -H), 3.76–3.66 (m, 2H, 3 -H, 4 -H), 3.74 (t,
1H, 6b-H), 3.69 (t, 1H, J4,5ˆ9.4 Hz, 4-H), 3.27 (d, 1H,
JˆϪ15.7 Hz, COCH2), 3.19 (d, 1H, JˆϪ15.8 Hz,
COCH2), 2.57–2.43 (m, 2H, SCH2CH3), 1.19 (t, 3H,
Jˆ7.4 Hz, SCH2CH3). 13C NMR (CDCl3): dˆ165.9, 164.1
(2 C, 2 C, NCO, COCH2), 101.4 (PhCH), 97.1 (C-1), 81.8
(C-10), 80.8 (C-4), 80.1 (C-30), 76.1 (C-20), 75.0 (PhCH2),
74.6 (C-40), 72.0, 71.9 (PhCH2), 69.9 (C-50), 69.8 (PhCH2),
68.7 (C-6), 67.3 (C-3), 64.2 (C-60), 62.9 (C-5), 54.0 (C-2),
41.1 (COCH2), 25.4 (SCH2CH3), 14.9 (SCH2CH3). Anal.
calcd for C60H59NO14S: C, 68.62; H, 5.66; N, 1.33; S,
3.05; Found: C, 68.69; H, 5.70; N, 1.39; S, 2.99.
Ethyl 2,3,4-tri-O-benzyl-6-O-[(1,6-di-O-benzyl-2-deoxy-
2-phthalimido-a-d-glucopyranos-3-yloxy)-carbonyl-
ethanoyl]-1-thio-a-d-mannopyranoside (13c). Et3SiH
(0.38 ml, 2.4 mmol) and CF3CO2H (0.24 ml, 2.4 mmol)
was added at 0ЊC to a solution of 12c (0.5 g, 0.48 mmol)
in dichloromethane (10 ml), the mixture was stirred at 20ЊC
for 2.5 h and concentrated. Chromatography (toluene/ethyl
acetate 5:1) of the residue afforded 13c (0.33 g, 65%),
Ethyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-benz-
yl-a-d-glucopyranos-3-yloxy)-carbonylethanoyl]-1-thio-
a-d-mannopyranoside (13a). Treatment of 12a (0.8 g,
0.78 mmol) in THF (15 ml) with NaCNBH3 (0.61 g,
9.75 mmol) and HCl in Et2O as described for the prepara-
tion of 3 and chromatography (toluene/acetone 15:1)
afforded 13a (0.63 g, 78%), [a]Dˆϩ81.9 (cˆ1.0, CHCl3).
1
[a]Dˆϩ115.1 (cˆ1.1, CHCl3). H NMR (CDCl3): dˆ6.62
0
0
0
(dd, 1H, J3,4ˆ9.0 Hz, 3-H), 5.29 (d, 1H, J1 ,2 ˆ1.2 Hz, 1 -H),
4.99 (d, 1H, J1,2ˆ3.6 Hz, 1-H), 4.88 (d, 1H, JˆϪ10.9 Hz,
PhCH2), 4.73 (d, 1H, JˆϪ12.6 Hz, PhCH2), 4.68 (d, 1H,
JˆϪ12.4 Hz, PhCH2), 4.64 (d, 1H, JˆϪ10.7 Hz, PhCH2),

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
571
4.60–4.53 (m, 5H, PhCH2), 4.45 (dd, 1H, J2,3ˆ11.5 Hz,
2-H), 4.44 (d, 1H, JˆϪ12.7 Hz, PhCH2), 4.28–4.21 (m,
2H, 6a0-H, 6b0-H), 4.18–4.03 (m, 2H, 5-H, 50-H), 3.85 (t,
(1.25 g, 95%) which was used without further purification in
the next step.
0
0
0
0
0
1H, J4 ,5 ˆ9.2 Hz, 4 -H), 3.81–3.78 (m, 2H, 2 -H, 3 -H),
3.76–3.71 (m, 3H, 4-H, 6a-H, 6b-H), 3.45 (bs, 1H, OH),
3.28 (s, 2H, COCH2), 2.59–2.45 (m, 2H, SCH2CH3), 1.20
(t, 3H, J 7.4 Hz, SCH2CH3). 13C NMR (CDCl3): dˆ167.6,
166.8, 166.1 (CO), 96.2 (C-1), 82.0 (C-10), 80.1 (C-30), 76.0
(C-20), 75.0 (PhCH2), 74.2 (C-40), 73.5 (PhCH2), 72.0 (2 C,
PhCH2), 71.8 (C-3), 71.4 (C-50), 71.1 (C-4), 69.8 (C-5), 69.4
(PhCH2), 68.9 (C-6), 64.5 (C-60), 53.8 (C-2), 41.3 (COCH2),
25.5 (SCH2CH3), 14.9 (SCH2CH3). Anal. calcd for
C60H61NO14S: C, 68.49; H, 5.84; N, 1.33; S, 3.05; Found:
C, 68.56; H, 5.88; N, 1.21; S, 3.20.
Phenyl 2,3,4-tri-O-benzyl-6-O-(3-hydroxycarbonylprop-
anoyl)-1-thio-a-d-mannopyranoside (14d). Treatment of
4
(1.02 g, 1.9 mmol), succinic anhydride (1.51 g,
15.04 mmol) and a catalytic amount of DMAP (ca. 0.1 g)
in pyridine (20 ml) at 20ЊC for 19 h as described for the
preparation of 10 and chromatography (CCl4/acetone 3:1)
afforded 14d (1.13 g, 94%), [a]Dˆϩ61.5 (cˆ1.0, CHCl3).
1H NMR (CDCl3): dˆ5.56 (d, 1H, J1,2ˆ1.5 Hz, 1-H), 4.94
(d, 1H, PhCH2), 4.72 (d, 1H, PhCH2), 4.64 (d, 1H, PhCH2),
4.61 (s, 2H, PhCH2), 4.59 (d, 1H, PhCH2), 4.40 (dd, 1H,
J5,6aˆ5.0 Hz, J6a,6bˆϪ11.9 Hz, 6a-H), 4.38–4.35 (m, 1H,
6b-H), 4.28 (ddd, 1H, J4,5ˆ9.2 Hz, J5,6bˆ2.2 Hz, 5-H),
4.00 (dd, 1H, J2,3ˆ2.8 Hz, 2-H), 3.98 (t, 1H, J3,4ˆ9.3 Hz,
4-H), 3.87 (dd, 1H, 3-H), 2.57 (s, 4H, CH2–CH2). 13C NMR
(CDCl3): dˆ176.9 (COOH), 171.8 (OCO–CH2), 85.6
(C-1), 80.1 (C-3), 76.2 (C-4), 75.3 (PhCH2), 74.5 (C-2),
72.1 (PhCH2), 70.9 (C-5), 63.6 (C-6), 28.9, 28.8 (CH2–
CH2). Anal. calcd for C37H38O8S: C, 69.14; H, 5.96; S,
4.99; Found: C, 68.95; H, 5.96; S, 4.76.
Phenyl 2,3,4-tri-O-benzyl-6-O-chlorocarbonyl-1-thio-a-
d-mannopyranoside (14a). Pyridine (0.19 ml, 2.3 ml)
and a solution of 4 (1.25 g, 2.3 mmol) in toluene (15 ml)
was added at Ϫ15ЊC to a 2.12 M solution of phosgene
in toluene (1.3 ml, 2.76 mmol) and the mixture was
stirred at 20ЊC for 17 h. Filtration of the mixture and
concentration of the filtrate afforded crude 14a (1.31 g,
94%) which was used without further purification for the
next step.
Phenyl 2,3,4-tri-O-benzyl-6-O-(2-chlorocarbonylbenzoyl)-
1-thio-a-d-mannopyranoside (14e). Pyridine (0.24 ml,
2.9 ml) and a solution of 4 (1.59 g, 2.93 mmol) in toluene
(5 ml) was added at 0ЊC to a solution of phthaloylchloride
(0.51 ml, 3.5 mmol) in toluene (15 ml) and the mixture was
stirred at 20ЊC for 15 h. Filtration of the mixture and
concentration of the filtrate afforded crude 14e (1.92 g,
93%) which was used without further purification for the
next step.
Phenyl 2,3,4-tri-O-benzyl-6-O-chlorooxalyl-1-thio-a-d-
mannopyranoside (14b). Pyridine (0.22 ml, 2.7 ml) and a
solution of 4 (1.47 g, 2.7 mmol) in toluene (30 ml) was
added at 0ЊC to a solution of oxalylchloride (0.28 ml,
3.25 mmol) in toluene (30 ml) and the mixture was stirred
at 20ЊC for 17 h. Filtration of the mixture and concen-
tration of the filtrate afforded crude 14b (1.72 g, 100%)
which was used without further purification for the next
step.
Phenyl 2,3,4-tri-O-benzyl-6-O-(2-hydroxycarbonylbenzoyl)-
1-thio-a-d-mannopyranoside (14e). Treatment of 4 (1.53
g, 2.8 mmol), phthalic anhydride (0.5 g, 3.38 mmol) and a
catalytic amount of DMAP (ca. 0.1 g) in pyridine (20 ml) at
20ЊC for 15 h as described for the preparation of 10 afforded
14e (1.75 g, 90%) which was used without further purifi-
cation for the next step.
Phenyl 2,3,4-tri-O-benzyl-6-O-(t-butyloxycarbonylethanoyl)-
1-thio-a-d-mannopyranoside (14c). Treatment of 4 (2.15
g, 4.0 mmol) and t-butyl malonate14 (0.63 g, 4.0 mmol) with
DCC (0.87 g, 4.23 mmol) in dichloromethane (40 ml) at
20ЊC for 16 h and workup as described for the preparation
of 8 and chromatography (n-hexane/ethyl acetate 10:1)
afforded 14c (1.64 g, 61%), [a]Dˆϩ71.6 (cˆ1.0, CHCl3).
1H NMR (CDCl3): dˆ5.55 (d, 1H, J1,2ˆ1.5 Hz, 1-H), 4.94
(d, 1H, JˆϪ10.7 Hz, PhCH2), 4.71 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.61 (d, 1H, JˆϪ12.2 Hz, PhCH2), 4.62 (d, 1H,
JˆϪ10.7 Hz, PhCH2), 4.60 (s, 2H, PhCH2), 4.44 (dd,
1H, J5,6aˆ5.3 Hz, J6a,6bˆϪ11.8 Hz, 6a-H), 4.37 (dd, 1H,
J5,6bˆ2.1 Hz, 6b-H), 4.33–4.28 (m, 1H, 5-H), 3.99 (dd,
1H, J2,3ˆ2.9 Hz, 2-H), 3.97 (t, 1H, J4,5ˆ9.3 Hz, 4-H), 3.87
(dd, 1H, J3,4ˆ9.2 Hz, 3-H), 3.26 (s, 2H, COCH2), 1.43 (s,
9H, C(CH3)3). 13C NMR (CDCl3): dˆ166.8 (COCH2),
165.5 (COCH2), 82.1 (C(CH3)3), 85.6 (C-1), 80.1 (C-3),
76.1 (C-2), 75.3 (PhCH2), 74.6 (C-4), 72.1 (PhCH2), 72.0
(PhCH2), 70.8 (C-5), 64.3 (C-6), 42.6 (COCH2), 27.9
(C(CH3)3). Anal. calcd for C40H44O8S: C, 70.15; H, 6.47;
S, 4.68; Found: C, 70.11; H, 6.56; S, 4.62.
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-carbo-
nyloxy]-1-thio-a-d-mannopyranoside (15a). A solution of
crude 14a (1.31 g, 2.17 mmol) in dichloromethane (15 ml)
was added at Ϫ10ЊC to a solution of 110 (1.0 g, 2.17 mmol)
in pyridine (20 ml), the mixture was stirred at 20ЊC for 20 h,
poured into water and extracted with dichloromethane. The
extracts were washed with aqueous HCl and NaHCO3 solu-
tion, dried and concentrated. Chromatography (toluene/
ethyl acetate 15:1) of the residue afforded 15a (1.81 g,
1
81%), [a]Dˆϩ93.3 (cˆ1.1, CHCl3). H NMR (CDCl3):
dˆ5.69 (t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.49 (s, 1H, PhCH),
0
0
0
5.41 (d, 1H, J1 ,2 ˆ1.4 Hz, 1 -H), 5.34 (d, 1H, J1,2ˆ3.8 Hz,
1-H), 5.01 (dd, 1H, J2,3ˆ9.9 Hz, 2-H), 4.74 (d, 1H,
JˆϪ10.4 Hz, PhCH2), 4.73 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.63 (d, 1H, JˆϪ12.5 Hz, PhCH2), 4.52 (d, 1H,
JˆϪ12.2 Hz, PhCH2), 4.50 (d, 1H, JˆϪ11.5 Hz, PhCH2),
4.43–4.33 (m, 2H, 6a0-H, 6b0-H), 4.32–4.15 (m, 3H,
PhCH2), 4.26 (dd, 1H, J5,6aˆ4.8 Hz, J5,6bˆ9.9 Hz,
Phenyl 2,3,4-tri-O-benzyl-6-O-(hydroxycarbonylethanoyl)-
1-thio-a-d-mannopyranoside (14c0). Trifluoroacetic acid
(3.2 ml, 41.8 mmol) was added at room temperature to a
solution of 14c (1.43 g, 2.1 mmol) in dichloromethane
(60 ml), the mixture was stirred for 2 h and concentrated.
Coevaporation of toluene (three times) afforded crude 14c0
J6a,6bˆϪ10.1 Hz, 6a-H), 4.21–4.15 (m, 1H, 50-H), 4.07
0
0
0
(dt, 1H, 5-H), 3.94 (t, 1H, J4 ,5 ˆ9.6 Hz, 4 -H), 3.91 (bd,
0
0
0
0
0
1H, J2 ,3 ˆ2.5 Hz, 2 -H), 3.80 (dd, 1H, J3 ,4 ˆ9.7 Hz,

572
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
30-H), 3.76–3.71 (m, 2H, J4,5ˆ9.9 Hz, 4-H, 6b-H). 13C
NMR (CDCl3): dˆ165.5 (PhCO), 154.6 (OCO), 101.6
(PhCH), 95.7 (C-1), 85.5 (C-10), 79.9 (C-30), 79.0 (C-4),
75.7 (C-20), 75.3 (PhCH2), 74.2 (C-40), 73.2 (C-3), 72.5
(C-2), 71.9 (PhCH2), 71.6 (PhCH2), 71.0 (C-50), 70.0
(PhCH2), 68.8 (C-6), 66.7 (C-60), 62.7 (C-5). Anal. calcd
for C61H58O13S: C, 71.05; H, 5.67; S, 3.11; Found: C, 71.16;
H, 5.69; S, 3.11.
ment of 14d (0.8 g, 1.24 mmol) and 110 (0.58 g,
1.24 mmol) with DCC (0.31 g, 1.49 mmol) and a catalytic
amount of DMAP in dichloromethane (20 ml) at 20ЊC for
22 h as described for the preparation of 8 and chromato-
graphy (CCl4/acetone 10:1) afforded 15d (1.25 g, 93%),
1
[a]Dˆϩ101.7 (cˆ1.2, CHCl3). H NMR (CDCl3): dˆ5.87
(t, 1H, J2,3ˆJ3,4ˆ9.9 Hz, 3-H), 5.56 (d, 1H, J1,2ˆ1.5 Hz,
1-H), 5.50 (s, 1H, PhCH), 5.27 (d, 1H, J1,2ˆ3.7 Hz, 1-H),
5.06 (dd, 1H, 2-H), 4.94–4.53 (8d, 8H, PhCH2-), 4.38–4.35
(m, 2H, 6a-H, 6b-H), 4.31–4.20 (m, 2H, 5-H, 5-H),
4.18–4.16 (m, 1H, 4-H), 3.99 (dd, 1H, J2,3ˆ2.9 Hz, 2-H),
3.98–3.93 (m, 1H, 4-H), 3.87 (dd, 1H, J3,4ˆ9.1 Hz, 3-H),
3.80–3.68 (m, 2H, J6a,6bˆϪ10.4 Hz, 6a-H, 6b-H), 2.53–
2.46 (m, 4H, CH2–CH2). 13C NMR (CDCl3): dˆ171.8,
171.6 (OCO–CH2), 165.8 (PhCO), 101.6 (PhCH), 95.9
(C-1), 85.5 (C-1), 80.1 (C-3), 79.1 (C-4), 76.1 (C-4), 75.9
(C-2), 75.3 (PhCH2), 74.5 (C-3), 72.3 (C-5), 72.1, 71.9, 69.9
(PhCH2), 69.2 (C-2), 68.8 (C-6), 63.6 (C-6), 62.8 (C-5),
28.9, 28.7 (CH2–CH2–). Anal. calcd for C64H62O14S: C,
70.70; H, 5.75; S, 2.95; Found: C, 70.46; H, 5.86; S, 2.76.
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-ox-
alyloxy]-1-thio-a-d-mannopyranoside (15b). Treatment
of crude 14b (1.72 g, 2.72 mmol) and 110 (1.26 g, 2.72
mmol) in pyridine (10 ml) at 20ЊC for 16 h as described
for the preparation of 15a afforded 15b (1.59 g, 55%),
1
[a]Dˆϩ103.7 (cˆ1.1, CHCl3). H NMR (CDCl3): dˆ5.94
(t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.54 (s, 1H, PhCH), 5.50 (d, 1H,
0
0
0
J1 ,2 ˆ1.4 Hz, 1 -H), 5.35 (d, 1H, J1,2ˆ3.8 Hz, 1-H), 5.07
(dd, 1H, J2,3ˆ9.9 Hz, 2-H), 4.75 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.73 (d, 1H, JˆϪ10.9 Hz, PhCH2), 4.67–4.59
(m, 5H, PhCH2), 4.54 (d, 1H, JˆϪ12.3 Hz, PhCH2),
4.40–4.21 (m, 4H, J5,6aˆ4.8 Hz, J6a,6bˆϪ10.2 Hz, 50-H,
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-2-car-
bonylbenzoyl]-1-thio-a-d-mannopyranoside (15e). Treat-
ment of crude 14e0 (1.24 g, 1.8 mmol), 110 (0.83 g,
1.8 mmol) and p-toluenesulfonic acid (30 mg, 0.18 mmol)
with DCC (0.37 g, 1.8 mmol) and a catalytic amount of
DMAP in pyridine (25 ml) at 20ЊC for 24 h as described
for the preparation of 8 and chromatography (CCl4/acetone
40:1) afforded 15e (1.43 g, 70%), [a]Dˆϩ94.0 (cˆ1.1,
6a-H, 6a0-H, 6b0-H), 4.12–4.05 (m, 1H, J5,6bˆ9.7 Hz,
0
0
0
5-H), 4.01 (dd, 1H, J2 ,3 ˆ2.6 Hz, 2 -H), 3.93 (t, 1H,
0
0
0
0
0
J4 ,5 ˆ9.2 Hz, 4 -H), 3.88–3.77 (m, 2H, J3 ,4 ˆ9.2 Hz,
J4,5ˆ9.7 Hz, 30-H, 4-H), 3.69 (t, 1H, 6b-H). 13C NMR
(CDCl3): dˆ165.5 (PhCO), 156.9, 156.3 (COCO), 101.7
(PhCH), 95.6 (C-1), 85.7 (C-10), 80.2 (C-30), 78.5 (C-4),
76.3 (C-20), 75.2 (PhCH2), 74.2 (C-40), 72.2 (C-2), 72.1
(PhCH2), 72.0 (PhCH2), 71.8 (C-50), 70.4 (C-3), 70.1
(PhCH2), 68.7 (C-6), 65.8 (C-60), 62.7 (C-5). Anal. calcd
for C62H58O14S: C, 70.31; H, 5.52; S, 3.03; Found: C, 70.22;
H, 5.55; S, 3.02.
1
CHCl3). H NMR (CDCl3): dˆ6.10 (t, 1H, J3,4ˆ9.8 Hz,
0
0
0
3-H), 5.57 (d, 1H, J1 ,2 ˆ1.5 Hz, 1 -H), 5.52 (s, 1H,
PhCH), 5.31 (d, 1H, J1,2ˆ3.8 Hz, 1-H), 5.14 (dd, 1H,
J2,3ˆ9.9 Hz, 2-H), 4.90 (d, 1H, JˆϪ10.6 Hz, PhCH2),
4.78 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.71 (d, 1H,
JˆϪ12.2 Hz, PhCH2), 4.64 (s, 3H, PhCH2), 4.63 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.55 (d, 1H, JˆϪ12.1 Hz, PhCH2),
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-car-
bonylethanoyl]-1-thio-a-d-mannopyranoside (15c).
Treatment of crude 14c0 (1.18 g, 1.9 mmol) and 110
(0.86 g, 1.87 mmol) with DCC (0.43 g, 2.06 mmol) and a
catalytic amount of DMAP in dichloromethane (40 ml) at
20ЊC for 14 h as described for the preparation of 8 and
chromatography (n-hexane/ethyl acetate 5:1) afforded 15c
4.35–4.22
(m,
4H,
J5,6aˆ4.7 Hz,
J5,6bˆ9.8 Hz,
J6a,6bˆϪ10.3 Hz, 50-H, 6a0-H, 6a-H, 6b0-H), 4.11 (dt, 1H,
0
0
0
5-H), 3.97 (t, 1H, J4 ,5 ˆ8.8 Hz, 4 -H), 3.88 (dd, 1H,
0
0
0
J3 ,4 ˆ9.2 Hz, 3 -H), 3.76–3.73 (m, 1H, J4,5ˆ9.8 Hz, 4-H),
3.75 (t, 1H, 6b-H). 31C NMR (CDCl3): dˆ167.0 (PhCO),
166.0, 165.8 (PhCOO), 101.3 (PhCH), 95.9 (C-1), 85.4
(C-10), 80.2 (C-30), 79.3 (C-4), 76.3 (C-20), 75.3 (PhCH2),
74.6 (C-40), 72.2 (C-2), 72.1, 72.0 (PhCH2), 70.9 (C-50),
70.1 (C-3), 69.9 (PhCH2), 68.8 (C-6), 63.9 (C-60), 62.8
(C-5). Anal. calcd for C68H62O14S: C, 71.94; H, 5.50; S,
2.82; Found: C, 71.82; H, 5.41; S, 2.90.
1
(1.44 g, 72%), [a]Dˆϩ104.1 (cˆ1.0, CHCl3). H NMR
(CDCl3): dˆ5.88 (t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.48 (d, 1H,
J1,2ˆ1.6 Hz, 10-H), 5.47 (s, 1H, PhCH), 5.29 (d, 1H,
J1,2ˆ3.8 Hz, 1-H), 5.05 (dd, 1H, J2,3ˆ9.9 Hz, 2-H), 4.88
(d, 1H, JˆϪ10.8 Hz, PhCH2), 4.73 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.67 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.63–4.57 (m,
3H, PhCH2), 4.53 (d, 1H, JˆϪ12.6 Hz, PhCH2), 4.52 (d,
1H, JˆϪ10.8 Hz, PhCH2), 4.27–4.15 (m, 4H, J5,6bˆ9.8 Hz,
50-H, 6a0-H, 6b0-H, 6a-H), 3.94 (bd, 1H, 20-H), 3.82–3.72
(m, 3H, 30-H, 40-H, 6b-H), 3.69 (t, 1H, J4,5ˆ9.7 Hz, 4-H),
3.26 (s, 2H, COCH2). 13C NMR (CDCl3): dˆ165.7 (CO),
165.6 (CO), 165.3 (CO), 101.5 (PhCH), 95.8 (C-1), 85.4
(C-10), 80.0 (C-30), 78.9 (C-4), 75.9 (C-20), 75.1 (PhCH2),
74.6 (C-40), 72.2 (C-2), 72.0 (2 C, PhCH2), 70.7 (C-50), 70.1
(C-3), 70.0 (PhCH2), 68.8 (C-6), 64.3 (C-60), 62.8 (C-5),
41.1 (COCH2). Anal. calcd for C64H60O14S: C, 70.51; H,
5.64; S, 2.99; Found: C, 70.37; H, 5.62; S, 3.09.
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-carbonyl]-1-thio-a-
d-mannopyranoside (16a). Treatment of 15a (1.06 g,
1.03 mmol) in THF (15 ml) with NaCNBH3 (0.58 g,
9.27 mmol) and HCl in Et2O as described for the prepara-
tion of 3 and chromatography (CCl4/acetone 12:1) afforded
16a (0.93 g, 87%), [a]Dˆϩ110.9 (cˆ1.0, CHCl3). 1H NMR
(CDCl3): dˆ5.45 (t, 1H, J3,4ˆ9.7 Hz, 3-H), 5.41 (d, 1H,
0
0
0
J1 ,2 ˆ1.4 Hz, 1 -H), 5.30 (d, 1H, J1,2ˆ3.7 Hz, 1-H), 4.97
(dd, 1H, J2,3ˆ10.2 Hz, 2-H), 4.92 (d, 1H, JˆϪ10.6 Hz,
PhCH2), 4.70 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.64 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.62 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.57 (d, 1H, JˆϪ10.6 Hz, PhCH2), 4.56 (d, 1H,
JˆϪ12.6 Hz, PhCH2), 4.51 (d, 1H, JˆϪ12.3 Hz, PhCH2),
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1-O-benzyl-
4,6-O-benzylidene-a-d-glucopyranos-3-yloxy)-3-car-bonyl-
propanoyl]-1-thio-a-d-mannopyranoside (15d). Treat-

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
573
0
0
4.50 (s, 3H, PhCH2), 4.47 (dd, 1H, J5 ,6a ˆ5.7 Hz,
(C-5,5), 69.6 (PhCH2), 69.3 (C-4), 69.1 (C-6), 64.7 (C-60),
41.5 (COCH2). Anal. calcd for C63H62O14S: C, 70.37; H,
5.81; S, 2.98; Found: C, 70.43; H, 5.93; S, 3.05.
0
0
0
0
0
J6a ,6b ˆϪ11.5 Hz, 6a -H), 4.38 (dd, 1H, J5 ,6b ˆ2.1 Hz,
6b0-H), 4.23 (ddd, 1H, 50-H), 3.99–3.91 (m, 3H,
0
0
0
0
J2 ,3 ˆ3.0 Hz, J4 ,5 ˆ9.8 Hz, J5,6aˆ4.3 Hz, J5,6bˆ3.7 Hz,
20-H, 40-H, 5-H), 3.86 (t, 1H, J4,5ˆ9.7 Hz, 4-H), 3.78 (dd,
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-3-carbonylpropa-
noyl]-1-thio-a-d-mannopyranoside (16d). Treatment of
15d (1.25 g, 1.15 mmol) in THF (20 ml) with NaCNBH3
(0.9 g, 14.4 mmol) and HCl in Et2O as described for the
preparation of 3 and chromatography (CCl4/acetone 5:1)
afforded 16d (1.04 g, 83%), [a]Dˆϩ98.3 (cˆ1.1, CHCl3).
1H NMR (CDCl3): dˆ5.65 (t, 1H, J2,3ˆJ3,4ˆ9.7 Hz, 3-H),
5.55 (d, 1H, J1,2ˆ1.4 Hz, 1-H), 5.23 (d, 1H, J1,2ˆ3.7 Hz,
1-H), 4.99 (dd, 1H, 2-H), 4.93 (d, 1H, PhCH2), 4.74 (d,
1H, PhCH2), 4.70 (d, 1H, PhCH2), 4.61–4.58 (m, 6H,
PhCH2, 5-H), 4.56 (d, 1H, PhCH2), 4.52 (d, 1H, PhCH2),
4.28–4.25 (m, 3H, J5,6aˆ4.9 Hz, J5,6bˆ2.6 Hz, 5-H, 6a-H,
6b-H), 3.97 (dd, 1H, 2-H), 3.92 (t, 1H, J3,4ˆ9.2 Hz, 4-H),
3.85 (dd, 1H, J2,3ˆ3.1 Hz, 3-H), 3.78–3.75 (m, 1H,
J4,5ˆ9.6 Hz, 4-H), 3.73 (dd, 1H, J5,6aˆ4.9 Hz,
J6a,6bˆϪ10.6 Hz, 6a-H), 3.69 (dd, 1H, J5,6bˆ3.2 Hz,
6b-H), 3.27 (d, 1H, J4,OHˆ3.7 Hz, OH), 2.64–2.43 (m, 4H,
CH2–CH2). 13C-NMR (CDCl3): dˆ172.2 (2, OCO–CH2),
165.7 (PhCO–), 95.2 (C-1), 85.4 (C-1), 80.0 (C-3), 76.1
(C-4), 75.2 (PhCH2), 74.4 (C-2), 73.6 (PhCH2), 73.5
(C-3), 72.1, 71.9 (PhCH2), 71.5 (C-4), 70.8 (C-5), 70.5
(C-2), 69.7 (C-5), 69.5 (PhCH2), 69.2 (C-6), 63.7 (C-6),
29.2 (2C, CH2–CH2). Anal. calcd for C64H64O14S: C,
70.57; H, 5.92; S, 2.94; Found: C, 70.72; H, 6.04; S, 2.79.
0
0
0
1H, J3 ,4 ˆ9.3 Hz, 3 -H), 3.75 (dd, 1H, J6a,6bˆϪ10.5 Hz, 6a-
H), 3.68 (dd, 1H, 6b-H), 2.72 (bs, 1H, OH). 13C NMR
(CDCl3): dˆ165.6 (PhCO), 155.4 (OCO), 95.1 (C-1), 85.5
(C-10), 79.9 (C-30), 76.9 (C-3), 75.7 (C-20), 75.3 (PhCH2),
74.5 (C-40), 73.7 (PhCH2), 71.9 (PhCH2), 71.7 (C-2), 71.6
(PhCH2), 70.9 (C-50), 70.1, 70.0 (C-4,5), 69.7 (PhCH2), 69.2
(C-6), 67.0 (C-60). Anal. calcd for C61H60O13S: C, 70.91; H,
5.85; S, 3.10; Found: C, 70.78; H, 5.96; S, 3.01.
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-oxalyloxy]-1-thio-a-
d-mannopyranoside (16b). Treatment of 15b (1.59 g,
1.5 mmol) in THF (20 ml) with NaCNBH3 (0.85 g,
13.5 mmol) and HCl in Et2O as described for the prepara-
tion of 3 and chromatography (CCl4/acetone 10:1) afforded
16b (0.35 g, 22%), [a]Dˆϩ118.2 (cˆ1.2, CHCl3). 1H NMR
(CDCl3): dˆ5.70 (t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.50 (d, 1H,
0
0
0
J1 ,2 ˆ1.4 Hz, 1 -H), 5.31 (d, 1H, J1,2ˆ3.7 Hz. 1-H), 5.03
(dd, 1H, J2,3ˆ10.0 Hz, 2-H), 4.89 (d, 1H, JˆϪ10.6 Hz,
PhCH2), 4.74 (d, 1H, JˆϪ12.5 Hz, PhCH2), 4.63 (d, 1H,
JˆϪ12.2 Hz, PhCH2), 4.60 (d, 1H, JˆϪ12.3 Hz, PhCH2),
4.55 (d, 1H, JˆϪ10.6 Hz, PhCH2), 4.53 (d, 1H,
JˆϪ10.6 Hz, PhCH2), 4.50 (d, 1H, JˆϪ12.3 Hz, PhCH2),
4.48 (bd, 3H, PhCH2), 4.46–4.27 (m0, 3H, 50-H, 6a0-H,
6b0-H), 4.05 (dd, 1H, J2 ,3 ˆ2.9 Hz, 2 -H), 4.00-3.93 (m,
1H, J5,6aˆ4.4 Hz, J5,6bˆ3.9 Hz, 5-H), 3.96 0 (t, 1H,
0
0
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-2-carbonylbenzoyl]-
1-thio-a-d-mannopyranoside (16e). Treatment of 15e
(0.48 g, 0.42 mmol) in THF (15 ml) with NaCNBH3
(0.33 g, 5.23 mmol) and HCl in Et2O as described for the
preparation of 3 and chromatography (CCl4/acetone 15:1)
afforded 16e (0.4 g, 83%), [a]Dˆϩ139.4 (cˆ1.0, CHCl3).
0
0
J4,5ˆ9.8 Hz, 4-H), 3.94 (t, 1H, J4 ,5 ˆ9.4 Hz, 4 -H), 3.81
(dd, 1H, J3 ,4 ˆ9.1 Hz, 30-H), 3.80 (dd, 1H,
J6a,6bˆϪ10.3 Hz, 6a-H), 3.63 (t, 1H, 6b-H), 2.75 (bs, 1H,
OH). 13C NMR (CDCl3): dˆ165.6 (PhCO), 157.4, 156.8
(COCO), 95.0 (C-1), 85.7 (C-10), 80.2 (C-30), 76.3 (C-20),
75.2 (PhCH2), 74.5 (C-40), 74.1 (C-3), 73.4 (PhCH2), 72.2,
72.1 (PhCH2), 71.7 (C-50), 71.4 (C-2), 70.0 (2 C, C-5,
PhCH2), 69.5 (C-4), 69.1 (C-6), 66.1 (C-60). Anal. calcd
for C62H60O14S: C, 70.17; H, 5.70; S, 3.02; Found: C,
70.04; H, 5.81; S, 2.91.
0
0
1H NMR (CDCl3): dˆ5.96 (t, 1H, J3,4ˆ10.0 Hz, 3-H), 5.59
0
0
0
(d, 1H, J1 ,2 ˆ1.4 Hz, 1 -H), 5.29 (d, 1H, J1,2ˆ3.7 Hz, 1-H),
5.05 (dd, 1H, J2,3ˆ10.2 Hz, 2-H), 4.96 (d, 1H, JˆϪ10.9 Hz,
PhCH2), 4.80 (d, 1H, JˆϪ12.4 Hz, PhCH2), 4.70 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.65–4.59 (m, 6H, PhCH2), 4.56 (d,
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-carbonylethanoyl]-1-
thio-a-d-mannopyranoside (16c). Treatment of 15c
(0.59 g, 0.55 mmol) in THF (15 ml) with NaCNBH3
(0.43 g, 6.9 mmol) and HCl in Et2O as described for the
preparation of 3 and chromatography (n-hexane/ethyl
acetate 3:1) afforded 16c (0.39 g, 73%), [a]Dˆϩ101.9
1H, JˆϪ12.7 Hz, PhCH2), 4.45–4.36 (m, 3H, 50-H, 6a0-H,
0
6b0-H), 4.06 (t, 1H, J4 ,5 ˆ9.5 Hz, 4 -H), 4.01–3.90 (m, 3H,
0
0
0
0
0
0
J3 ,4 ˆ9.5 Hz, 3 -H, 4 -H, 5-H), 3.89 (t, 1H, J4,5ˆ9.7 Hz,
4-H), 3.80–3.67 (m, 3H, 6a-H, 6b-H, OH). 13C NMR
(CDCl3): dˆ168.5 (PhCO), 166.5, 165.7 (PhCOO), 95.2
(C-1), 85.3 (C-10), 80.2 (C-3), 76.2, 74.8 (C-20,4), 75.3
(PhCH2), 74.3 (C-30), 73.5 (PhCH2), 72.1, 72.0 (PhCH2),
71.5 (C-2), 70.8 (2 C, C-50, C-5), 69.0 (C-4), 68.8 (C-6),
64.6 (C-60). Anal. calcd for C68H64O14S: C, 71.81; H, 5.67;
S, 2.82; Found: C, 71.70; H, 5.80; S, 2.95.
(cˆ1.0, CHCl3). 1H NMR (CDCl3): dˆ5.65 (dd, 1H,
0
0
0
J3,4ˆ9.2 Hz, 3-H), 5.52 (d, 1H, J1 ,2 ˆ1.5 Hz, 1 -H), 5.24
(d, 1H, J1,2ˆ3.7 Hz, 1-H), 4.97 (dd, 1H, J2,3ˆ10.2 Hz,
2-H), 4.90–4.83 (m, 4H, PhCH2), 4.73 (d, 1H,
JˆϪ12.6 Hz, PhCH2), 4.65–4.55 (m, 4H, PhCH2), 4.51
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-carbonyl]-1-sulfoxy-
a-d-mannopyranoside (17a). A solution of 16a (207 mg,
0.2 mmol) and 55% m-chloroperbenzoic acid (87 mg,
0.28 mmol) in dichloromethane (10 ml) was stirred at
20ЊC for 24 h and concentrated. Chromatography (toluene/
ethyl acetate 5:1) of the residue afforded 17a (168 mg,
(d, 1H, JˆϪ12.5 Hz, PhCH2), 4.33–4.24 (m, 3H, 50-H,
6a0-H, 6b0-H), 3.97–3.95 (m, 2H, J2 ,3 ˆ2.8 Hz, 2 -H,
0
0
0
0
0
0
5-H), 3.94 (t, 1H, J4 ,5 ˆ9.2 Hz, 4 -H), 3.84 (dd, 1H,
0
0
0
J3 ,4 ˆ9.2 Hz, 3 -H), 3.71–3.63 (m, 3H, 4-H, 6a-H, 6b-H),
3.57 (d, 1H, J4,OHˆ3.2 Hz, OH), 3.29 (bd, 2H, COCH2). 13
C
NMR (CDCl3): dˆ167.0 (PhCO), 165.8 (COCH2), 165.7
(COCH2), 95.0 (C-1), 85.5 (C-10), 80.0 (C-30), 76.0
(C-20), 75.3 (PhCH2), 74.6, 74.3 (C-3,4), 73.6 (PhCH2),
72.1 (PhCH2), 72.0 (PhCH2), 71.4 (C-2), 70.6, 70.7
1
80%), [a]Dˆϩ38.2 (cˆ1.0, CHCl3). H NMR (CDCl3):
dˆ5.45 (dd, 1H, J3,4ˆ8.7 Hz, 3-H), 5.28 (d, 1H,
J1,2ˆ3.7 Hz, 1-H), 5.03 (dd, 1H, J2,3ˆ10.2 Hz, 2-H), 4.90

574
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
0
0
0
0
0
(d, 1H, JˆϪ10.9 Hz, PhCH2), 4.72 (d, 1H, JˆϪ12.3 Hz,
PhCH2), 4.65 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.59 (d, 1H,
JˆϪ12.2 Hz, PhCH2), 4.57 (bs, 4H, PhCH2), 4.55 (d, 1H,
JˆϪ11.2 Hz, PhCH2), 4.47 (d, 1H, JˆϪ11.5 Hz, PhCH2),
J3 ,4 ˆ8.6 Hz, 3 -H), 4.10 (bd, 2H, 6a -H, 6b -H), 3.98-
3.91 (m, 1H, 50-H), 3.83 (t, 1H, J4 ,5 ˆ9.2 Hz, 4 -H),
3.80–3.70 (m, 3H, 5-H, 6a-H, 6b-H), 3.67–3.63 (m, 1H,
4-H), 3.17 (d, 1H, J4,OHˆ3.7 Hz, OH), 2.60–2.38 (m, 4H,
COCH2CH2). 13C NMR (CDCl3): dˆ172.2, 172.0
(COCH2CH2), 165.7 (PhCO), 95.2 (C-1), 90.8 (C-10), 79.2
(C-30), 74.4 (2 C, C-50, PhCH2), 73.9 (C-40), 73.7 (PhCH2),
73.5 (C-3), 73.2 (PhCH2), 72.8 (PhCH2), 71.4 (2 C, C-2,
C-20), 70.4 (C-5), 69.9 (C-4), 69.6 (PhCH2), 69.3 (C-6),
63.9 (C-60), 29.1 (2 C, COCH2CH2). Anal. calcd for
C64H64O15S: C, 69.55; H, 5.84; S, 2.90; Found: C, 69.85;
H, 5.77; S, 2.98.
0
0
0
4.43 (s, 1H, 10-H), 4.40 (dd, 1H, J5 ,6a ˆ2.0 Hz, J6a ,6b
ˆ
0
0
0
0
0
Ϫ11.7 Hz, 6a0-H), 4.31 (bt, 1H, J2 ,3 ˆ3.2 Hz, 2 -H), 4.24
0
0
0
0
0
0
0
(dd, 1H, J5 ,6b ˆ6.6 Hz, 6b -H), 4.09 (dd, 1H, J3 ,4 ˆ9.0 Hz,
30-H), 4.05–4.00 (m, 1H, 50-H), 3.98–3.89 (m, 2H,
J5,6aˆ3.9 Hz, J5,6bˆ3.6 Hz, 4-H, 5-H), 3.85 (t, 1H,
J4 ,5 ˆ9.3 Hz, 40-H), 3.78 (dd, 1H, J6a,6bˆϪ10.4 Hz,
6a-H), 3.70 (dd, 1H, 6b-H), 2.86 (d, 1H, J4,OHˆ3.9 Hz,
OH). 13C NMR (CDCl3): dˆ165.5 (PhCO), 155.2 (OCO),
95.2, 95.1 (C-1,10), 79.0 (C-30), 77.1 (C-3), 75.8 (C-50), 75.0
(PhCH2), 73.7 (PhCH2), 73.4 (C-40), 72.3 (PhCH2), 72.0
(PhCH2), 71.6 (C-2), 71.2 (C-20), 70.1 (2 C, C-4, C-5),
69.7 (PhCH2), 69.2 (C-6), 67.2 (C-60). Anal. calcd for
C61H60O14S: C, 69.83; H, 5.76; S, 3.06; Found: C, 69.49;
H, 5.85; S, 3.09.
0
0
General procedure A: According to Table 2, a solution of
13a–c or 16a–e and 4 A molecular sieves in MeCN or
˚
dichloromethane were stirred under Ar for 0.5 h and cooled
to Ϫ30ЊC. NIS and TMSOTf were added at Ϫ30ЊC, the
mixture was stirred for 10 min, neutralized by addition of
pyridine, diluted with dichloromethane and filtered. The
filtrate was washed with aqueous NaHCO3 and Na2S2O3
solution, dried and concentrated. Chromatography (toluene/
ethyl acetate) of the residue afforded compounds 18a,b,f
and 19a–c,f.
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-oxalyloxy]-1-sulfoxy-
a-d-mannopyranoside (17b). Treatment of 16b (218 mg,
0.21 mmol) and 55% m-chloroperbenzoic acid (89 mg,
0.28 mmol) in dichloromethane (10 ml) as described for
the preparation of 17a afforded 17b (183 mg, 83%),
General procedure B: According to Table 2, a solution of
13a–c and 16a,b and MeOTf in MeCN or dichloromethane
was stirred at 20ЊC for 6 h, neutralized by addition of Et3N,
diluted with dichloromethane and filtered. The filtrate was
washed with water, dried and concentrated. Chromato-
graphy (toluene/ethyl acetate) of the residue afforded
compounds 18a,b and 19a–c.
1
[a]Dˆϩ90.8 (cˆ1.4, CHCl3). H NMR (CDCl3): dˆ5.68
(t, 1H, J3,4ˆ9.9 Hz, 3-H), 5.29 (d, 1H, J1,2ˆ3.7 Hz, 1-H),
5.11 (dd, 1H, J2,3ˆ10.0 Hz, 2-H), 4.80 (d, 1H, JˆϪ10.9 Hz,
PhCH2), 4.73 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.65 (d, 1H,
JˆϪ12.2 Hz, PhCH2), 4.63 (d, 1H, JˆϪ11.9 Hz, PhCH2),
4.62–4.56 (m, 3H, PhCH2), 4.55 (d, 1H, JˆϪ12.0 Hz,
0
0
0
PhCH2), 4.53 (d, 1H, J1 ,2 ˆ1.5 Hz, 1 -H), 4.51 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.49 (d, 1H, JˆϪ12.3 Hz, PhCH2),
General procedure C: According to Table 2, a solution of
IDCP and 13b and 16a,b in MeCN or dichloromethane was
stirred at 20ЊC until all starting material was consumed. The
mixture was diluted with dichloromethane, filtered, and the
filtrate was washed with aqueous Na2S2O3 solution, dried
and concentrated. Chromatography (toluene/ethyl acetate)
of the residue afforded 18b and 19b.
0
0
0
0
4.41 (dd, 1H, J2 ,3 ˆ3.3 Hz, 2 -H), 4.39–4.18 (m, 2H, 6a -H,
6b0-H), 4.12 (dd, 1H, J3 ,4 ˆ9.3 Hz, 3 -H), 4.16–3.98 (m,
0
0
0
1H, 50-H), 4.04 (t, 1H, J4,5ˆ9.7 Hz, 4-H), 4.02–3.95 (m,
1H, J5,6aˆ4.3 Hz, J5,6bˆ3.5 Hz, 5-H), 3.85 (t, 1H,
0
0
0
J4 ,5 ˆ9.6 Hz, 4 -H), 3.83 (dd, 1H, J6a,6bˆϪ10.2 Hz, 6a-
H), 3.61 (t, 1H, 6b-H), 2.80 (bs, 1H, OH). 13C NMR
(CDCl3): dˆ165.7 (PhCO), 157.2, 156.6 (COCO), 95.1
(C-1), 94.3 (C-10), 79.2 (C-30), 74.5 (2 C, C-50, PhCH2),
74.4 (C-3), 74.1 (C-40), 73.4 (PhCH2), 73.1 (PhCH2), 71.2
(PhCH2), 72.0 (C-20), 71.1 (C-2), 70.1 (C-5), 70.0 (PhCH2),
69.6 (C-4), 69.1 (C-6), 66.4 (C-60). Anal. calcd for
C62H60O15S: C, 69.13; H, 5.61; S, 2.98; Found: C, 69.00;
H, 5.74; S, 3.05.
General procedure D: According to Table 2, a solution of
16a,b and DMTST in MeCN or dichloromethane was stirred
at 20ЊC until all starting material was consumed. TLC
showed complete decomposition of the starting material.
General procedure E: According to Table 2, AgOTf was
added at 20ЊC to a solution of 16a,b in MeCN or dichloro-
methane. Br2 was added and the mixture was stirred until all
starting material was consumed. TLC showed complete
decomposition of the starting material.
Phenyl 2,3,4-tri-O-benzyl-6-O-[(2-O-benzoyl-1,6-di-O-
benzyl-a-d-glucopyranos-3-yloxy)-3-carbonylpropa-
noyl]-1-sulfoxy-a-d-mannopyranoside (17c). Treatment
of 16d (0.69 g, 0.63 mmol) and 55% m-chloroperbenzoic
acid (0.25 g, 0.78 mmol) in dichloromethane (10 ml) as
described for the preparation of 17a afforded 17c (0.59 g,
General procedure F: According to Table 2, Tf2O was
added under Ar at Ϫ50ЊC to a solution of 17a–c and 2,6-
di-t-butylpyridine in MeCN or dichloromethane. The
mixture was warmed to 20ЊC, stirred for 50 h, diluted with
dichloromethane and filtered. The filtrate was washed with
aqueous NaHCO3 solution dried and concentrated. Chroma-
tography (toluene/ethyl acetate) of the residue afforded
18b,d,e and 19b.
1
84%), [a]Dˆϩ69.2 (cˆ1.1, CHCl3). H NMR (CDCl3):
dˆ5.63 (dd, 1H, J3,4ˆ9.3 Hz, 3-H), 5.22 (d, 1H,
J1,2ˆ3.8 Hz, 1-H), 5.00 (dd, 1H, J2,3ˆ10.2 Hz, 2-H), 4.85
0
0
(d, 1H, JˆϪ11.2 Hz, PhCH2), 4.77 (d, 1H, J1 ,2 ˆ1.7 Hz,
10-H), 4.71 (d, 1H, JˆϪ10.6 Hz, PhCH2), 4.69 (d, 1H,
JˆϪ12.8 Hz, PhCH2), 4.65 (bs, 2H, PhCH2), 4.62 (d, 1H,
JˆϪ12.3 Hz, PhCH2), 4.61 (d, 1H, JˆϪ11.5 Hz, PhCH2),
4.57 (bd, 1H, J2 ,3 ˆ3.3 Hz, 20-H), 4.55 (d, 1H,
JˆϪ12.3 Hz, PhCH2), 4.52 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.49 (d, 1H, JˆϪ11.0 Hz, PhCH2), 4.26 (dd, 1H,
Benzyl O-(2,3,4-tri-O-benzyl-a-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-malonate
(18a). [a]Dˆϩ140.1 (cˆ1.0, CHCl3). H NMR (CDCl3):
0
0
1

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
575
Table 2. Intramolecular glycosylation of compounds 13, 16 and 17 according to the general procedures A–F
Starting material
(mg, mmol)
Solvent
(ml)
Proc.
Activators
(g or ml, mmol)
Products, yield
(mg, %)
13a (460, 0.45)
13a (410, 0.40)
MeCN (15)
CH2Cl2 (15)
A
A
NIS (0.50, 2.24), TMSOTf (20,
0.11)
NIS (0.45, 2.00), TMSOTf (18,
0.1)
18a (58, 13), 19a (250, 58)
18a (64, 17), 19a (204, 53)
13a (460, 0.45)
13a (520, 0.51)
13b (470, 0.45)
MeCN (15)
CH2Cl2 (15)
MeCN (15)
B
B
A
MeOTf (340, 3.14)
MeOTf (280, 2.53)
NIS (0.51, 2.25), TMSOTf (20,
0.11)
18a (28, 6), 19a (315, 73)
18a (46, 9), 19a (335, 68)
18b (169, 38), 19b (146, 33)
13b (400, 0.39)
CH2Cl2 (15)
A
NIS (0.44, 1.94), TMSOTf (18,
0.1)
18b (164, 43), 19b (104, 27)
13b (640, 0.62)
13b (390, 0.37)
13b (380, 0.37)
13b (360, 0.34)
13c (300, 0.29)
MeCN (15)
CH2Cl2 (10)
MeCN (10)
CH2Cl2 (10)
MeCN (10)
B
B
C
C
A
MeOTf (340, 3.14)
MeOTf (200, 1.87)
IDCP (0.35, 0.74)
IDCP (0.32, 0.69)
NIS (0.32, 1.43), TMSOf (13,
0.07)
18b (161, 27), 19b (257, 43)
18b (112, 31), 19b (133, 37)
18b (129, 36), 19b (132, 37)
18b (133, 40), 19b (106, 32)
19c (144, 51)
13c (310, 0.30)
CH2Cl2 (12)
A
NIS (0.34, 1.50), TMSOf (14,
0.08)
19c (140, 47)
13c (400, 0.38)
13c (350, 0.33)
16a (214, 0.21)
MeCN (12)
CH2Cl2 (12)
MeCN (20)
B
B
A
MeOTf (214, 1.92)
MeOTf (128, 1.67)
NIS (0.23, 1.04), TMSOTf (5,
0.052)
NIS (0.29, 1.29), TMSOTf (12,
0.065)
MeOTf (90, 0.81)
MeOTf (110, 1.03)
IDCP (150, 0.31)
IDCP (210, 0.45)
DMTST (290, 1.12)
DMTST (230, 0.87)
AgOTf (124, 0.48), Br2 (8.7,
0.17)
19c (199, 52)
19c (160, 49)
–
a
a
16a (250, 0.26)
CH2Cl2 (20)
A
–
b
16a (166, 0.16)
16a (213, 0.21)
16a (157, 0.15)
16a (225, 0.22)
16a (240, 0.24)
16a (199, 0.19)
16a (250, 0.25)
MeCN (10)
CH2Cl2 (10)
MeCN (8)
CH2Cl2 (12)
MeCN (15)
CH2Cl2 (10)
MeCN (15)
B
B
C
C
D
D
E
–
–
–
–
–
–
–
b
b
b
a
a
a
a
16a (155, 0.15)
CH2Cl2 (10)
E
AgOTf (80, 0.30), Br2 (5.5,
0.11)
–
17a (350, 0.37)
17a (149, 0.14)
16b (350, 0.33)
MeCN (20)
CH2Cl2 (10)
MeCN (10)
F
F
A
Tf2O (182, 2.2)
Tf2O (66, 0.43)
NIS (0.37, 1.65), TMSOTf (15,
0.083)
NIS (0.32, 1.41), TMSOTf (13,
0.072)
MeOTf (152, 1.39)
MeOTf (135, 1.23)
IDCP (268, 0.57)
IDCP (248, 0.53)
DMTST (362, 1.4)
DMTST (307, 1.19)
AgOTf (142, 0.55), Br2 (10,
0.20)
18d (257, 76)
18d (103, 79)
–
a
a
16b (300, 0.28)
CH2Cl2 (10)
A
–
a
16b (294, 0.28)
16b (261, 0.25)
16b (303, 0.29)
16b (280, 0.26)
16b (330, 0.31)
16b (280, 0.26)
16b (294, 0.28)
MeCN (10)
CH2Cl2 (10)
MeCN (10)
CH2Cl2 (12)
MeCN (12)
CH2Cl2 (12)
MeCN (12)
B
B
C
C
D
D
E
–
–
–
–
–
–
–
a
b
b
a
a
a
a
16b (237, 0.22)
CH2Cl2 (12)
E
AgOTf (115, 0.45), Br2 (8.0,
0.16)
–
17a (320, 0.30)
17a (282, 0.26)
16c (211, 0.20)
MeCN (18)
CH2Cl2 (10)
MeCN (15)
F
F
A
Tf2O (146, 0.89)
Tf2O (129, 0.79)
NIS (0.22, 0.98), TMSOTf (15,
0.083)
18e (204, 72)
18e (187, 75)
18a (42, 22), 19a (102, 54)
16c (364, 0.38)
16d (520, 0.48)
16c (370, 0.34)
CH2Cl2 (20)
MeCN (60)
CH2Cl2 (50)
A
A
A
NIS (0.42, 1.89), TMSOTf (17,
0.094)
NIS (0.54, 2.40), TMSOTf (20,
0.11)
NIS (0.38, 1.70), TMSOTf (14,
0.08)
18a (90, 25), 19a (180, 50)
18b (213, 45), 19b (118, 25)
18b (175, 53), 19a (71, 21)
17c (330, 0.30)
17c (300, 0.27)
16e (290, 0.26)
MeCN (10)
CH2Cl2 (10)
MeCN (15)
F
F
A
Tf2O (132, 0.60)
Tf2O (119, 0.54)
NIS (0.29, 1.30), TMSOTf (12,
0.065)
18b (142, 48), 19b (67, 23)
18b (144, 54), 19b (61, 23)
18f (183, 69), 19f (23, 9)
16e (340, 0.30)
CH2Cl2 (15)
A
NIS (0.34, 1.51), TMSOTf (14,
0.08)
18f (195, 63), 19f (31, 10)
a Decomposition of the starting material.
b No reaction.

576
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
dˆ5.77 (t, 1H, J3,4ˆ10.0 Hz, 3-H), 5.11 (d, 1H,
J1,2ˆ3.4 Hz, 1-H), 4.93 (dd, 1H, J2,3ˆ9.6 Hz, 2-H), 4.92
(s, 1H, 10-H), 4.87 (d, 1H, JˆϪ11.4 Hz, PhCH2), 4.84–
4.80 (m, 1H, 6a0-H), 4.82 (d, 1H, JˆϪ11.2 Hz, PhCH2),
4.81 (d, 1H, JˆϪ10.9 Hz, PhCH2), 4.75–4.66 (m, 4H,
PhCH2), 4.54 (d, 1H, JˆϪ12.6 Hz, PhCH2), 4.51 (s, 1H,
PhCH2), 4.43 (d, 1H, JˆϪ12.2 Hz, PhCH2), 4.11 (t, 1H,
(C-5), 68.8 (C-6), 67.0 (C-60). Anal. calcd for C55H34O13: C,
71.57; H, 5.90; Found: C, 71.64; H, 5.88.
Benzyl O-(2,3,4-tri-O-benzyl-a-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-
1
oxalate (18e). [a]Dˆϩ128.6 (cˆ2.13, CHCl3). H NMR
(CDCl3): dˆ5.98 (t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.18 (d, 1H,
J4,5ˆ10.4 Hz, 4-H), 4.11–4.04 (m, 1H, 50-H), 3.77–3.71
J1,2ˆ3.6 Hz, 1-H), 4.99 (dd, 1H, J2,3ˆ9.9 Hz, 2-H), 4.90
0
0
(m, 1H, 6b0-H), 3.73 (dd, 1H, J3 ,4 ˆ9.3 Hz, 3 -H), 3.64
(d, 1H, J1 ,2 ˆ1.3 Hz, 1 -H), 4.88 (d, 1H, JˆϪ10.7 Hz,
PhCH2), 4.76 (d, 1H, JˆϪ11.8 Hz, PhCH2), 4.66 (d, 1H,
JˆϪ11.8 Hz, PhCH2), 4.59 (d, 1H, JˆϪ12.5 Hz, PhCH2),
4.56 (d, 1H, JˆϪ10.7 Hz, PhCH2), 4.53 (d, 1H,
JˆϪ11.0 Hz, PhCH2), 4.52–4.46 (m, 4H, PhCH2), 4.42 (t,
1H, J4,5ˆ9.9 Hz, 4-H), 4.33–4.14 (m, 1H, 6a0-H), 4.04–3.93
0
0
0
0
(t, 1H, J4 ,5 ˆ9.3 Hz, 40-H), 3.50–3.44 (m, 1H,
0
0
0
0
J5,6bˆ4.0 Hz, 5-H), 3.43–3.39 (m, 2H, J2 ,3 ˆ3.0 Hz,
J6a,6bˆϪ10.9 Hz, 20-H, 6a-H), 3.33–3.28 (m, 1H, 6b-H),
3.27 (d, 1H, JˆϪ12.6 Hz, COCH2), 3.18 (d, 1H,
JˆϪ12.6 Hz, COCH2). 13C NMR (CDCl3): dˆ165.6
(COCH2), 165.4 (COCH2), 164.5 (PhCO), 94.8 (C-1), 93.1
(m, 2H, 50-H, 6b0-H), 3.78–3.72 (m, 1H, J5,6aˆ4.2 Hz, 5-H),
(C-10, JC-1 ,1 -Hˆ166.0 Hz), 79.3 (C-30), 75.5 (C-40), 75.3
(C-20), 74.5 (PhCH2), 73.5 (PhCH2), 73.2 (C-4), 73.0
(C-2), 72.8 (PhCH2), 72.5 (PhCH2), 69.5 (PhCH2), 69.1,
68.9 (C-3,5,5), 68.8 (C-6), 64.8 (C-60), 43.3 (COCH2).
Anal. calcd for C57H56O14: C, 70.94; H, 5.85; Found: C,
70.60; H, 5.85.
3.74 (dd, 1H, J3 ,4 ˆ9.2 Hz, 3 -H), 3.67 (t, 1H, J4 ,5 ˆ9.3 Hz,
0
0
0
0
0
0
0
40-H), 3.55–3.48 (m, 1H, J2 ,3 ˆ3.0 Hz, 2 -H), 3.54 (dd, 1H,
J6a,6bˆϪ10.7 Hz, 6a-H), 3.30–3.24 (m, 1H, 6b-H). 13C
NMR (CDCl3): dˆ165.8 (PhCO), 157.6, 156.7 (COCO),
0
0
0
94.8 (C-1), 93.9 (C-10, JC-1 ,1 -Hˆ165.6 Hz), 79.3 (C-30),
75.4 (PhCH2), 74.8 (C-20), 73.4, 73.3 (C-4,4), 73.2
(PhCH2), 73.1 (C-2), 72.0, 71.9 (PhCH2), 71.8 (C-50), 69.8
(PhCH2), 69.1 (C-3), 68.7 (C-6), 68.2 (C-5), 66.2 (C-60).
Anal. calcd for C56H54O14 (951.04): C, 70.72; H, 5.72;
Found: C, 70.86; H, 5.69.
0
0
Benzyl O-(2,3,4-tri-O-benzyl-a-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-succi-
nate (18b). [a]Dˆϩ119.1 (cˆ1.0; CHCl3). 1H NMR
(CDCl3): dˆ6.05 (t, 1H, J2,3ˆJ3,4ˆ10.0 Hz, 3-H), 5.14 (d,
1H, J1,2ˆ3.4 Hz, 1-H); 5.05 (d, 1H, J1,2ˆ1.6 Hz, 1-H), 4.92
(dd, 1H, 2-H), 4.86 (d, 1H, PhCH2), 4.78 (d, 1H, PhCH2),
4.60–4.52 (m, 6H, PhCH2), 4.45 (d, 1H, PhCH2), 4.42 (d,
1H, PhCH2), 4.26–4.14 (m, 3H, J6a,6bˆϪ10.6 Hz, 5-H,
6a-H, 6b-H), 4.02 (dt, 1H, J4,5ˆ9.3 Hz, 5-H), 3.66–3.56
(m, 2H, 2-H, 4-H), 3.75 (dd, 1H, J2,3ˆ2.9 Hz, J3,4ˆ8.6 Hz,
3-H), 3.50–3.43 (m, 2H, 4-H, 6a-H), 3.36 (dd, 1H, 6b-H),
2.87–2.59 (m, 2H, CH2–CH2), 2.42–2.34 (m, 1H, CH2–
CH2), 2.17–2.09 (m, 1H, CH2–CH2). 13C NMR (CDCl3):
dˆ171.5, 170.4 (O–CO–CH2), 165.7 (PhCO–), 95.0
(C-1), 92.8 (C-1, JC-1,1-Hˆ164.5 Hz), 80.0 (C-4), 79.2
(C-5), 75.2 (C-2), 74.8 (PhCH2), 73.6 (PhCH2), 73.2
(C-3), 72.8 (C-3), 72.5 (PhCH2), 72.3 (PhCH2), 71.0
(C-2), 70.8 (C-5), 69.7 (PhCH2), 68.6 (C-6), 67.4 (C-4),
64.2 (C-6), 29.9, 29.7 (CH2-CH2). Anal. calcd for
C58H58O14: C, 71.15; H, 5.97; Found: C, 70.94; H, 5.97.
Benzyl O-(2,3,4-tri-O-benzyl-a-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-
phthalate (18f). [a]Dˆϩ153.6 (cˆ1.36, CHCl3). 1H NMR
(CDCl3): dˆ6.35 (t, 1H, J3,4ˆ9.8 Hz, 3-H), 5.20 (d, 1H,
J1,2ˆ3.4 Hz, 1-H), 5.15 (dd, 1H, J2,3ˆ9.3 Hz, 2-H), 5.14
0
0
0
(d, 1H, J1 ,2 ˆ1.7 Hz, 1 -H), 4.86 (d, 1H, JˆϪ11.1 Hz,
PhCH2), 4.80 (d, 1H, JˆϪ12.6 Hz, PhCH2), 4.73 (d, 1H,
JˆϪ10.4 Hz, PhCH2), 4.71 (d, 1H, JˆϪ12.4 Hz, PhCH2),
4.69 (d, 1H, JˆϪ11.2 Hz, PhCH2), 4.61 (d, 1H,
JˆϪ12.4 Hz, PhCH2), 4.59 (d, 1H, JˆϪ11.2 Hz, PhCH2),
4.57 (d, 1H, JˆϪ12.7 Hz, PhCH2), 4.54 (d, 1H,
JˆϪ11.6 Hz, PhCH2), 4.52 (s, 1H, PhCH2), 4.44–4.41
(m, 1H, J6a ,6b ˆϪ10.3 Hz, 6a0-H), 4.31 (t, 0 1H,
0
0
0
0
0
J5 ,6b ˆ10.3 Hz, 6b -H), 4.08–3.98 (m, 2H, 4-H, 5 -H),
3.94–3.75 (m, 2H, 40-H, 5-H), 3.69 (dd, 1H, J3 ,4 ˆ5.9 Hz,
0
0
30-H), 3.62–3.42 (m, 3H, J2 ,3 ˆ2.9 Hz, 2 -H, 6a-H, 6b-H).
0
0
0
13C NMR (CDCl3): dˆ167.5 (PhCO), 165.9, 165.7
(PhCOO), 94.8 (C-1), 93.9 (C-10, JC-1 ,1 -Hˆ164.3 Hz),
75.7 (C-30), 75.3, 74.6 (C-20,4), 73.6 (C-40), 73.4
(PhCH2), 73.0 (C-2), 72.6, 72.5, 72.1 (PhCH2), 71.3
(C-50), 69.8 (PhCH2), 69.6 (C-5), 68.3 (C-3), 68.2 (C-6),
64.9 (C-60). Anal. calcd for C62H58O14: C, 72.50; H, 5.69;
Found: C, 72.32; H, 5.74.
0
0
Benzyl O-(2,3,4-tri-O-benzyl-a-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-car-
1
bonate (18d). [a]Dˆϩ121.7 (cˆ0.99, CHCl3). H NMR
(CDCl3): dˆ5.73 (t, 1H, J3,4ˆ9.9 Hz, 3-H), 5.17 (d, 1H,
J1,2ˆ3.7 Hz, 1-H), 4.93 (dd, 1H, J2,3ˆ10.1 Hz, 2-H), 4.81
(s, 1H, 10-H), 4.78 (d, 1H, JˆϪ11.0 Hz, PhCH2), 4.69 (d,
1H, JˆϪ12.3 Hz, PhCH2), 4.66 (d, 1H, JˆϪ11.7 Hz,
PhCH2), 4.60 (d, 1H, JˆϪ11.8 Hz, PhCH2), 4.59 (d, 1H,
JˆϪ12.5 Hz, PhCH2), 4.55 (d, 1H, JˆϪ11.7 Hz, PhCH2),
Benzyl O-(2,3,4-tri-O-benzyl-b-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-malo-
nate (19a). [a]Dˆϩ80.3 (cˆ1.2, CHCl3). 1H NMR
(CDCl3): dˆ5.74 (t, 1H, J3,4ˆ9.5 Hz, 3-H), 5.26 (d, 1H,
J1,2ˆ3.8 Hz, 1-H), 5.00 (dd, 1H, J2,3ˆ10.1 Hz, 2-H), 4.91
(d, 1H, JˆϪ11.3 Hz, PhCH2), 4.81 (d, 1H, JˆϪ12.6 Hz,
PhCH2), 4.73 (d, 1H, JˆϪ12.5 Hz, PhCH2), 4.70 (d, 1H,
4.53 (d, 1H, JˆϪ12.6 Hz, PhCH2), 4.50 (s, 3H, PhCH2),
0
0
0
0
0
4.34 (dd, 1H, J5 ,6a ˆ1.7 Hz, J6a ,6b ˆϪ11.5 Hz, 6a -H),
4.30 (t, 1H, J4,5ˆ9.4 Hz, 4-H), 4.04–4.00 (m, 1H,
0
0
0
0
J5 ,6b ˆ4.9 Hz, 5 -H), 3.95 (dd, 1H, 6b -H), 3.77–3.71 (m,
0
0
0
1H, 5-H), 3.67 (dd, 1H, J3 ,4 ˆ9.4 Hz, 3 -H), 3.65 (t, 1H,
0
0
0
0
0
J4 ,5 ˆ8.9 Hz, 4 -H), 3.49 (bd, 1H, 6a-H), 3.45–3.35 (m,
JˆϪ12.6 Hz, PhCH2), 4.64–4.60 (m, 1H, J6a ,6b
ˆ
J2 ,3 ˆ2.5 Hz, 2 -H), 3.32 (bd, 1H, 6b-H). 13C NMR
Ϫ11.3 Hz, 6a0-H), 4.58 (d, 1H, JˆϪ11.3 Hz, PhCH2),
4.56 (d, 1H, JˆϪ12.3 Hz, PhCH2), 4.55 (d, 1H,
JˆϪ12.5 Hz, PhCH2), 4.49 (s, 2H, PhCH2), 4.29 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.22 (s, 1H, 10-H), 4.01 (dd, 1H,
6b0-H), 3.97 (t, 1H, J4,5ˆ9.5 Hz, 4-H), 3.81–3.78 (m, 1H,
0
0
0
(CDCl3): dˆ165.3 (PhCO), 154.1 (OCO), 94.9 (C-1), 93.7
(C-10, JC-1 ,1 -Hˆ168.5 Hz), 79.0 (C-30), 74.4 (PhCH2), 74.2
(C-20), 74.0 (C-4), 73.8 (PhCH2), 73.4, 73.3 (C-2,40), 73.0,
72.5 (PhCH2), 71.9 (C-3), 71.0 (C-50), 70.5 (PhCH2), 68.2
0
0

G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
577
0
0
0
J5,6aˆ1.8 Hz, 5-H), 3.78 (t, 1H, J4 ,5 ˆ9.3 Hz, 4 -H), 3.60
(CDCl3): dˆ6.06 (dd, 1H, J3,4ˆ9.5 Hz, 3-H), 5.32 (d, 1H,
J1,2ˆ3.5 Hz, 1-H), 5.12 (dd, 1H, J2,3ˆ10.2 Hz, 2-H), 4.98
(d, 1H, JˆϪ10.8 Hz, PhCH2), 4.85 (d, 1H, JˆϪ12.5 Hz,
PhCH2), 4.75 (d, 1H, JˆϪ11.5 Hz, PhCH2), 4.70 (d, 1H,
0
0
0
0
0
(ddd, 1H, J5 ,6a ˆ4.8 Hz, J5 ,6b ˆ7.8 Hz, 5 -H), 3.54 (bd,
0
0
0
1H, J2 ,3 ˆ3.0 Hz, 2 -H), 3.41 (dd, 1H, J6a,6bˆϪ10.9 Hz,
6a-H), 3.39–30.33 (m, 1H, 6b-H), 3.34 (dd, 1H,
0
0
J3 ,4 ˆ9.0 Hz, 3 -H), 3.28 (d, 1H, JˆϪ12.4 Hz, COCH2),
3.18 (d, 1H, JˆϪ12.4 Hz, COCH2). 13C NMR (CDCl3):
dˆ165.9 (COCH2), 165.5 (COCH2), 164.3 (PhCO), 103.2
JˆϪ11.7 Hz, PhCH2), 4.68–4.58 (m, 3H, PhCH2), 4.55 (s,
0
0
0
2H, PhCH2), 4.48–4.44 (m, 1H, J6a ,6b ˆ11.4 Hz, 6a -H),
4.34 (s, 1H, 10-H), 4.43 (d, 1H, JˆϪ12.5 Hz, PhCH2),
(C-10, JC-1 ,1 -Hˆ153.2 Hz), 95.0 (C-1), 82.3 (C-30), 78.4
(C-4), 76.6 (C-40), 74.9 (PhCH2), 73.6 (2 C, PhCH2), 71.9
(PhCH2), 69.7 (PhCH2), 74.2 (C-20), 72.6 (C-3), 72.2 (C-2),
70.2 (C-50), 69.8 (C-5), 67.9 (C-6), 64.1 (C-60), 42.9
(COCH2). Anal. calcd for C57H56O14: C, 70.94; H, 5.85;
Found: C, 70.77; H, 5.88.
4.33 (dd, 1H, J5 ,6b ˆ9.0 Hz, 6b0-H), 4.18 (t, 1H,
0
0
0
0
0
0
0
J4,5ˆ9.4 Hz, 4-H), 3.92 (t, 1H, J4 ,5 ˆ9.5 Hz, 4 -H), 3.91–
3.82 (m, 1H, 5-H), 3.68–3.60 (m, 1H, 50-H), 3.62–3.56 (m,
0
0
0
0
2H, J2 ,3 ˆ2.7 Hz, 2 -H, 3 -H), 3.52–3.44 (m, 2H, 6a-H,
6b-H). 13C NMR (CDCl3): dˆ168.3 (PhCO), 165.2, 164.2
(PhCOO), 102.4 (C-10, JC-1 ,1 -Hˆ153.4 Hz), 95.2 (C-1), 79.0
(C-3), 77.7 (C-4), 76.9 (C-30), 75.9, 74.7 (C-2,40), 75.1
(PhCH2), 73.9, 73.5, 72.2 (PhCH2), 71.3 (C-2), 70.2 (C-5),
69.5 (PhCH2), 69.1 (C-50), 67.8 (C-6), 64.1 (C-60). Anal.
calcd for C62H58O14: C, 72.50; H, 5.69; Found: C, 72.34;
H, 5.75.
0
0
Benzyl O-(2,3,4-tri-O-benzyl-b-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-succi-
nate (19b). [a]Dˆϩ38.8 (cˆ1.0, CHCl3). 1H NMR
(CDCl3): dˆ5.83 (dd, 1H, J2,3ˆ9.9 Hz, J3,4ˆ8.8 Hz, 3-H),
5.22 (d, 1H, J1,2ˆ3.6 Hz, 1-H), 5.00 (dd, 1H, 2-H), 4.90 (d,
1H, PhCH2), 4.79 (d, 1H, PhCH2), 4.69 (d, 1H, PhCH2),
4.62–4.50 (m, 6H, 1-H, PhCH2), 4.37–4.29 (m, 2H,
PhCH2), 4.26–4.16 (m, 2H, 6a-H, 6b-H), 4.02 (t, 1H,
J3,4ˆJ4,5ˆ9.3 Hz, 4-H), 3.82 (d, 1H, J2,3ˆ3.1 Hz, 2-H),
3.72 (t, 1H, J4,5ˆ9.5 Hz, 4-H), 3.53–3.42 (m, 3H, 3-H,
5-H, 5-H), 3.36 (dd, 1H, J5,6aˆ6.7 Hz, 6a-H), 3.32–3.26
(m, 1H, J5,6bˆ2.8 Hz, 6b-H), 2.73–2.24 (m, 4H, CH2–
CH2). 13C NMR (CDCl3): dˆ171.0, 170.7 (O–CO–CH2),
165.7 (PhCO), 103.0 (C-1, JC-1,1-Hˆ153.1 Hz), 95.2 (C-1),
82.7 (C-4), 78.5 (C-5), 75.5 (C-2), 75.2 (PhCH2), 74.6 (C-3),
73.9 (PhCH2), 73.5 (PhCH2), 72.7 (C-3), 72.4 (C-2), 72.2
(C-5), 72.0 (PhCH2), 69.9 (C-4), 69.7 (PhCH2), 68.1 (C-6),
63.4 (C-6), 30.3, 29.8 (CH2–CH2). Anal. calcd for
C58H58O14: C, 71.15; H, 5.97; Found: C, 70.97; H, 6.01.
Benzyl O-(6-O-benzoyl-2,3,4-tri-O-benzyl-a-d-manno-
pyranosyl)-(1!4)-2,3-di-O-benzoyl-6-O-benzyl-a-d-
glucopyranoside (20). (a) A solution of 18a (90 mg,
0.09 mmol) and a catalytic amount of NaOMe in methanol
(8 ml) was stirred at 20ЊC for 3 h, neutralized with Dowex
ion exchange resin (Hϩ form) and concentrated. The residue
was dissolved in pyridine (8 ml) and benzoyl chloride
(0.065 ml, 0.56 mmol) was added. The mixture was stirred
at 20ЊC for 24 h, poured into water and extracted with
dichloromethane. The extracts were washed with aqueous
HCl and NaHCO3 solution, dried and concentrated. Chro-
matography (n-hexane/ethyl acetate 4:1) of the residue
afforded 20 (71.7 mg, 70%), [a]Dˆϩ57.7 (cˆ0.52,
1
CHCl3). H NMR (CDCl3): dˆ6.07 (dd, 1H, J3,4ˆ8.9 Hz,
3-H), 5.32 (d, 1H, J1,2ˆ3.7 Hz, 1-H), 5.16 (dd, 1H,
0
0
0
Benzyl O-(2,3,4-tri-O-benzyl-b-d-mannopyranosyl)-(1!4)-
1,6-di-O-benzyl-2-deoxy-2-phthalimido-a-d-gluco-
pyranoside-3,6-malonate (19c). [a]Dˆϩ86.8 (cˆ1.20,
J2,3ˆ10.3 Hz, 2-H), 5.14 (d, 1H, J1 ,2 ˆ1.7 Hz, 1 -H), 4.87
(d, 1H, JˆϪ10.8 Hz, PhCH2), 4.79 (d, 1H, JˆϪ12.4 Hz,
PhCH2), 4.61 (d, 1H, JˆϪ11.6 Hz, PhCH2), 4.59 (s, 1H,
PhCH2), 4.58 (d, 1H, JˆϪ10.6 Hz, PhCH2), 4.57 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.55–4.52 (m, 1H, PhCH2), 4.51 (dd,
1
CHCl3). H NMR (CDCl3): dˆ6.51 (dd, 1H, J3,4ˆ8.2 Hz,
3-H), 4.95 (d, 1H, J1,2ˆ4.0 Hz, 1-H), 4.93 (d, 1H,
JˆϪ11.1 Hz, PhCH2), 4.90 (d, 1H, JˆϪ12.7 Hz, PhCH2),
4.72 (d, 1H, JˆϪ12.7 Hz, PhCH2), 4.71 (d, 1H,
0
0
0
0
1H, J6a ,6b ˆϪ11.8 Hz, 6a -H), 4.45–4.41 (m, 2H, 6b -H,
0
0
0
PhCH2), 4.13 (t, 1H, J4 ,5 ˆ9.4 Hz, 4 -H), 4.06–4.00 (m,
JˆϪ12.8 Hz, PhCH2), 4.67–4.60 (m, 2H, J2,3ˆ11.1 Hz,
2H, J5,6bˆ2.0 Hz, 5-H, PhCH2), 4.03 (t, 1H, J4,5ˆ9.5 Hz,
0
0
0
0
0
0
0
J6a ,6b ˆϪ11.4 Hz, 2-H, 6a -H), 4.59 (d, 1H, JˆϪ12.7 Hz,
PhCH2), 4.57 (d, 1H, JˆϪ11.2 Hz, PhCH2), 4.47–4.44 (m,
2H, PhCH2), 4.40 (d, 1H, JˆϪ11.9 Hz, PhCH2), 4.32 (d,
4-H), 3.96–3.91 (m, 2H, J5 ,6a ˆ3.1 Hz, 3 -H, 5 -H), 3.89–
3.83 (m, 1H, J6a,6bˆϪ11.1 Hz, 6a-H), 3.72 (dd, 1H, 6b-H),
3.60 (t, 1H, J2 ,3 ˆ2.4 Hz, 2 -H). 13C NMR (CDCl3):
0
0
0
1H, JˆϪ12.1 Hz, PhCH2), 4.26 (s, 1H, 10-H), 4.09 (dd, 1H,
dˆ166.3, 165.6, 165.5 (PhCO), 100.2 (C-10, JC-1 ,1 -
0
0
0
J5 ,6b ˆ6.0 Hz, 6b -H), 4.03–3.97 (m, 2H, 4-H, 5-H), 3.82 (t,
ˆ171.8 Hz), 95.1 (C-1), 79.6 (C-30), 76.7 (C-40), 75.6
0
0
H
0
0
1H, J4 ,5 ˆ9.4 Hz, 4 -H), 3.57 (bd, 1H, J2 ,3 ˆ2.9 Hz, 2 -H),
(C-20), 75.1 (PhCH2), 73.7 (C-4), 73.5 (PhCH2), 72.9
(C-3), 72.5 (PhCH2), 71.8 (C-2), 71.6 (PhCH2), 71.4
(C-50), 70.2 (C-5), 69.8 (PhCH2), 68.6 (C-6), 63.5 (C-60).
Anal. calcd for C68H64O14: C, 73.90; H, 5.84; Found: C,
73.95; H, 5.83. (b) Treatment of 18b (198 mg, 0.2 mmol)
as described under (A) afforded 20 (175 mg, 78%). (c)
Treatment of 18d (92 mg, 0.1 mmol) as described under
(A) afforded 20 (81.7 mg, 74%). (d) Treatment of 18e
(86 mg, 0.09 mmol) as described under (A) afforded 20
(69.9 mg, 70%). (e) Treatment of 18f (99 mg,
0.096 mmol) as described under (A) afforded 20 (74.7 mg,
70%).
0
0
0
0
3.47 (bs, 2H, 6a-H, 6b-H), 3.44–3.41 (m, 1H, 50-H), 3.26
0
0
0
(dd, 1H, J3 ,4 ˆ9.3 Hz, 3 -H), 3.20 (d, 1H, JˆϪ12.1 Hz,
COCH2), 3.12 (d, 1H, JˆϪ12.1 Hz, COCH2). 13C NMR
(CDCl3): dˆ167.3, 166.3 (COCH2), 163.4 (2 C, NCO),
102.3 (C-10, JC-1 ,1 -Hˆ157.7 Hz), 96.3 (C-1), 82.0 (C-30),
78.1 (C-4), 75.9 (C-40), 75.0 (PhCH2), 73.7 (2 C, PhCH2,
C-20), 73.5 (PhCH2), 71.4 (PhCH2), 70.6 (C-50), 70.4
(C-3), 70.0 (C-5), 69.5 (PhCH2), 68.1 (C-6), 63.4 (C-
60), 53.8 (C-2), 42.9 (COCH2). Anal. calcd for
C58H55NO14: C, 70.36; H, 5.60; N, 1.42; Found: C, 70.07;
H, 5.64; N, 1.28.
0
0
Benzyl O-(2,3,4-tri-O-benzyl-b-d-mannopyranosyl)-(1!4)-
2-O-benzoyl-6-O-benzyl-a-d-glucopyranoside-3,6-
phthalate (19f). [a]Dˆϩ80.9 (cˆ1.68, CHCl3). H NMR
Benzyl O-(6-O-benzoyl-2,3,4-tri-O-benzyl-b-d-mannopy-
ranosyl)-(1!4)-2,3-di-O-benzoyl-6-O-benzyl-a-d-gluco-
pyranoside (21a). (A) Treatment of 19a (324 mg,
1

578
G. Lemanski, T. Ziegler / Tetrahedron 56 (2000) 563–579
0.34 mmol) as described for the preparation of 20 under (A)
afforded 21a (283 mg, 76%), [a]DˆϪ45.6 (cˆ1.22,
References
1
CHCl3). H NMR (CDCl3): dˆ6.07 (t, 1H, J3,4ˆ9.8 Hz,
1. Barresi, F.; Hindsgaul, O. Synthesis of b-d-Mannose Contain-
ing Oligosaccharides. Modern Methods in Carbohydrate Synthesis;
Khan, S. H., O’Neill, R. A., Eds.; Harwood Academic Publishers:
Amsterdam, 1996; pp 251–276.
3-H), 5.33 (d, 1H, J1,2ˆ3.8 Hz, 1-H), 5.18 (dd, 1H,
J2,3ˆ10.2 Hz, 2-H), 4.89 (d, 1H, JˆϪ12.0 Hz, PhCH2),
4.79 (d, 1H, JˆϪ10.9 Hz, PhCH2), 4.75 (d, 1H,
JˆϪ12.7 Hz, PhCH2), 4.65 (d, 1H, JˆϪ12.1 Hz, PhCH2),
4.56 (d, 1H, JˆϪ12.5 Hz, PhCH2), 4.51 (d, 1H,
JˆϪ11.8 Hz, PhCH2), 4.44 (bd, 2H, JˆϪ11.8 Hz, 10-H,
PhCH2), 4.42 (bd, 2H, JˆϪ11.7 Hz, PhCH2), 4.39 (d, 1H,
2. (a) Paulsen, H.; Lockhoff, O. Chem. Ber. 1981, 114, 3102–
3114. (b) Paulsen, H.; Kutschker, W.; Lockhoff, O. Chem. Ber.
1981, 114, 3233–3241.(c) Crich, D.; Sun, S. J. Org. Chem.
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1998, 39, 5721–5724.
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Int. Ed. Engl. 1994, 33, 1765–1767. (d) Dan, A.; Ito, Y.; Ogawa, T.
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T.; Kuramochi, K.; Dan, A.; Ogawa, T.; Ito, Y. Eur. J. Org. Chem.
1999, 1367–1376.
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38, 3413–3414. (b) Schmidt, R. R.; Moering, U.; Reichrath, M.
Chem. Ber. 1982, 115, 39–49. (c) Hodosi, G.; Kovac, P. J. Am.
Chem. Soc. 1997, 119, 2335–2336.
8. Ziegler, T.; Lemanski, G. Angew. Chem. 1998, 110, 3367–
3369; Angew. Chem., Int. Ed. Engl. 1998, 37, 3129–3132.
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36, 8973–8976.
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Perkin Trans. 1 1993, 1453–1460.
JˆϪ10.8 Hz, PhCH2), 4.22 (t, 1H, J4,5ˆ9.8 Hz, 4-H), 4.13
0
0
0
(dd, 1H, J6a ,6b ˆϪ11.7 Hz, 6a -H), 4.08–4.02 (m, 2H, 5-H,
6b0-H), 3.76 (t, 1H, J4 ,5 ˆ9.4 Hz, 4 -H), 3.70–3.60 (m, 3H,
0
0
0
J2 ,3 ˆ2.7 Hz, 20-H, 6a0-H, 6b-H), 3.32 (bdd, 2H,
0
0
J3 ,4 ˆ9.2 Hz, J5 ,6a ˆ2.0 Hz, 20-H, 50-H). 13C NMR
0
0
0
0
(CDCl3): dˆ166.0, 165.7, 165.6 (PhCO), 100.8 (C-10,
JC-1 ,1 -Hˆ156.8 Hz), 95.3 (C-1), 82.1 (C-30), 75.1
(C-4), 75.0 (PhCH2), 74.1 (2 C, C-20, C-40), 73.7
(PhCH2), 73.5 (2 C, C-50, PhCH2), 72.0 (C-2), 71.2
(PhCH2), 70.2, 70.1 (C-3,5), 69.8 (PhCH2), 68.2 (C-6),
63.5 (C-60). Anal. calcd for C68H64O14: C, 73.90; H,
5.84; Found: C, 73.92; H, 5.90. (B) Treatment of 19b
(105 mg, 0.11 mmol) as described under (A) afforded
21a (88 mg, 75%). (C) Treatment of 19f (89 mg,
0.087 mmol) as described under (A) afforded 21a
(69.5 mg, 73%).
0
0
Benzyl O-(6-O-benzoyl-2,3,4-tri-O-benzyl-b-d-mannopy-
ranosyl)-(1!4)-3-O-benzoyl-6-O-benzyl-2-deoxy-2-
phthalimido-a-d-glucopyranoside (21b). (A) Treatment
of 19c (125 mg, 0.13 mmol) as described for the preparation
of 20 under (A) afforded 21b (104 mg, 73%), [a]Dˆϩ8.4
(cˆ1.14, CHCl3). 1H NMR (CDCl3): dˆ6.84 (dd, 1H,
J3,4ˆ9.3 Hz, 3-H), 5.02 (d, 1H, J1,2ˆ3.5 Hz, 1-H), 4.90 (d,
1H, JˆϪ11.3 Hz, PhCH2), 4.88 (d, 1H, JˆϪ12.5 Hz,
PhCH2), 4.82 (dd, 1H, J2,3ˆ11.1 Hz, 2-H), 4.74 (d, 1H,
JˆϪ12.4 Hz, PhCH2), 4.66 (d, 1H, JˆϪ12.5 Hz, PhCH2),
4.55 (d, 1H, JˆϪ12.6 Hz, PhCH2), 4.53 (d, 1H,
JˆϪ12.1 Hz, PhCH2), 4.48 (s, 1H, 10-H), 4.46–4.41 (m,
2H, PhCH2), 4.38 (d, 1H, JˆϪ12.0 Hz, PhCH2), 4.30–
4.23 (m, 2H, 4-H, 5-H), 4.22 (d, 1H, JˆϪ12.1 Hz,
0
0
0
PhCH2), 4.18–4.11 (m, 1H, J6a ,6b ˆϪ12.0 Hz, 6a -H),
4.13 (dd 1H, J5 ,6b ˆ4.8 Hz, 6b0-H), 3.80 (t, 1H,
0
0
0
0
0
J4 ,5 ˆ9.3 Hz, 4 -H), 3.73 (bd, 2H, 6a-H, 6b-H), 3.68 (bd,
0
0
0
0
0
0
1H, J2 ,3 ˆ3.0 Hz, 2 -H), 3.24 (dd, 1H, J3 ,4 ˆ9.2 Hz, 3 -H),
3.20–3.13 (m, 1H, 50-H). 13C NMR (CDCl3): dˆ166.1,
165.8 (PhCO), 163.4 (2 C, NCO), 100.2 (C-10, JC-1 ,1 -
13. Ottoson, H. Carbohydr. Res. 1990, 197, 101–107.
14. Backer, H. J.; Homan, J. D. H. Recl. Trav. Chim. Pays-Bas
1939, 58, 1048–1061.
15. Ziegler, T.; Ritter, A.; Hu¨rttlen, J. Tetrahedron Lett. 1997, 38,
3715–3718.
16. (a) Saigo, K.; Usui, M.; Kikuchi, K.; Shimada, E.;
Mukaiyama, T. Bull. Chem. Soc. Jpn. 1977, 50, 1863–1866. (b)
Mukaiyama, T. Angew. Chem. 1979, 91, 798–812; Angew. Chem.,
Int. Ed. Engl. 1979, 18, 707–721.
0
0
ˆ154.8 Hz), 96.6 (C-1), 81.8 (C-30), 75.2 (PhCH2), 74.8
H
(C-4), 73.9 (C-50), 73.7 (C-40), 73.6 (2 C, C-20, PhCH2),
72.9 (C-3), 72.1 (PhCH2), 70.4 (C-5), 69.6 (PhCH2), 68.4
(C-6), 62.8 (C-60), 54.0 (C-2). Anal. calcd for C69H63NO14:
C, 73.33; H, 5.62; N, 1.24; Found: C, 73.16; H, 5.58; N,
1.10.
17. DeNinno, M. P.; Etienne, J. B.; Duplantier, K. C. Tetrahedron
Lett. 1995, 36, 669–672.
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We thank Dr H. Schmickler, and C. Schmitz, University of
Cologne for performing the NMR spectra and elemental
analyses. This work was financially supported by the
Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie.
¨
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jugate J. 1987, 4, 97–108. (b) Lonn, H. Carbohydr. Res. 1985,

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