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L. Chen, F. Kong / Carbohydrate Research 338 (2003) 2169ꢀ2175
/
3.11. Methyl 2,3,4,6-tetra-O-benzoyl-a-
mannopyranosyl-(103)-2,4,6-tri-O-benzoyl-a-
mannopyranosyl-(102)-[2,3,4,6-tetra-O-benzyl-a-
glucopyranosyl-(103)]-4,6-di-O-benzoyl-a-
mannopyranosyl-(102)-3,4,6-tri-O-benzoyl-a-
mannopyranosyl-(102)-3,4,6-tri-O-benzoyl-a-
mannopyranoside (14)
D
-
etherꢀ
85%): [a]2D0
8.25ꢀ7.05 (m, 75 H, PhH), 6.14 (dd, 1 H, J3,4
9.9 Hz, H-4 of Manp), 6.02ꢀ5.90 (m, 3 H, H-4 of
Manp), 5.80 (dd, 1 H, J2,3 3.3 Hz, H-3 of Manp), 5.68
(m, 2 H), 5.61 (dd, 1 H, H-2 of Manp), 5.45 (dd, 1 H, H-
2 of Manp), 5.23 (s, 1 H, H-1 of Manp), 5.21 (s, 1 H, H-
1 of Manp), 5.18 (s, 1 H, H-1 of Manp), 5.10 (d, 1 H,
J1,2 1.4 Hz, H-1 of Manp), 5.08 (s, 1 H, H-1 of Manp),
4.94 (dd, 1 H, H-3 of Manp), 4.90 (d, 1 H, J1,2 4.0 Hz,
/
EtOAc) gave 15 as an amorphous solid (0.30 g,
26.78 (c 1.0, CHCl3); 1H NMR (CDCl3): d
J4,5
/
D
-
ꢃ
/
/
D
-
/
ꢄ
/
ꢄ
/
/
D-
/
/
D
-
-
/
D
Donor 12 (0.63 g, 0.30 mmol) and acceptor 139 (0.29 g,
0.30 mmol) were dried together under high vacuum for 2
h, then dissolved in anhyd CH2Cl2 (40 mL). TMSOTf
H-1 of Glcp), 4.63ꢀ
/
3.87 (m, 22 H), 3.93 (s, 3 H, CH3O),
3.34 (m, 4 H), 1.80 (bs, 4 H, OH); 13C NMR
(10 mL, 0.05 mmol) was added at ꢃ
/
25 8C with nitrogen
3.42ꢀ
/
protection. The reaction mixture was stirred for 3 h, at
the end of which time TLC indicated that the reaction
was complete. Then the mixture was neutralized with
Et3N and concentrated under reduced pressure to
dryness. Purification by column chromatography (2:1
(CDCl3): d 166.78, 166.73, 166.45, 166.39, 166.37,
166.31, 165.98, 165.80, 165.80, 165.50, 165.46, 165.42,
164.99, 164.99, 164.83 (15 PhCO), 133.71, 133.63,
133.39, 133.25, 133.13, 130.31, 130.17, 130.05, 129.96,
129.85, 129.80, 129.20, 128.71, 128.53, 128.46, 128.26
petroleum etherꢀ
70%): [a]2D0 47.08 (c 1.0, CHCl3); 1H NMR (CDCl3): d
8.14ꢀ7.02 (m, 95 H, PhH), 6.14 (dd, 1 H, J3,4 J4,5
10.0 Hz, H-4 of Manp), 6.02 (dd, 1 H, J3,4 J4,5 9.9
Hz, H-4 of Manp), 5.96ꢀ5.90 (m, 4 H), 5.80 (dd, 1 H,
/
EtOAc) gave 14 as a syrup (0.61 g,
(Phꢁ
/
C), 102.05, 100.92, 100.92, 100.11, 100.03, 99.49 (6
ꢃ
/
C-1), 81.49, 78.79, 75.35, 74.11, 71.11, 72.65, 72.29,
71.92, 70.77, 69.93, 69.70, 69.47, 69.32, 68.75, 68.30,
67.86, 66.95, 66.77, 66.02, 63.95, 63.42, 63.10, 61.59 (C-
/
ꢄ
/
ꢄ
/
ꢄ
/
ꢄ
/
/
2ꢀ/6), 55.35 (CH3O). Anal. Calcd for C142H124O46: C,
J2,3 2.8 Hz, H-3 of Manp), 5.74 (m, 2 H, H-3 of Manp),
5.37 (m, 3 H, 2 H-1 and H-2 of Manp), 5.28 (s, 1 H, H-1
of Manp), 5.25 (d, 1 H, J1,2 2.9 Hz, H-1 of Glcp), 5.08
(s, 1 H, H-1 of Manp), 5.00 (s, 1 H, H-1 of Manp),
66.46; H, 4.84. Found: C, 66.68; H, 4.93.
3.13. Methyl a-
D
-mannopyranosyl-(10
2)-[a-
-glucopyranosyl-(10
-mannopyranosyl-(102)-a- -mannopyranosyl-(10
-mannopyranoside (16)
/
3)-a-D-
4.76ꢀ
/
3.79 (m, 32 H), 3.68 (dd, 1 H), 3.36 (m, 1 H), 3.33
mannopyranosyl-(10
D
/
D
/
3)]-a-
(s, 3 H, CH3O); 13C NMR (CDCl3): d 166.18, 166.01,
165.87, 165.77, 165.53, 165.50, 165.25, 165.25, 164.04,
165.04, 164.98, 164.82, 164.82, 164.62, 164.33 (15
PhCO), 138.79, 138.49, 138.06, 137.84, 133.23, 133.03,
132.88, 132.78, 129.79, 129.71, 129.56, 129.44, 129.33,
129.26, 128.31, 128.20, 128.07, 127.90, 127.84, 127.66,
/
D
/2)-
a-D
Compound 15 (0.23 g, 0.09 mmol) was dissolved in a
satd solution of NH3 in anhyd CH3OH (10 mL). After a
week at rt, the reaction mixture was concentrated, and
the residue was purified by chromatography on Sepha-
127.42 (Phꢁ
/
C), 101.55, 100.54, 99.61, 99.37, 99.09, 97.52
(6 C-1), 81.59, 78.28, 78.12, 77.88, 77.19, 75.21, 74.77,
74.54, 73.05, 71.83, 71.42, 71.21, 71.04, 70.93, 70.61,
70.08, 69.90, 69.36, 69.01, 68.86, 68.49, 68.29, 67.82,
dex LH-20 (MeOH) to afford 16 as a syrup (77 mg,
1
85%): [a]2D0
5.16 (2 s, 2 H, H-1 of Manp), 5.15 (d, 1 H, J1,2 4.0 Hz,
H-1 of Glcp), 5.03 (2 s, 2 H, H-1 of Manp), 4.89 (s, 1 H,
ꢁ
/
29.68 (c 0.9, CHCl3); H NMR (D2O): d
67.70, 67.01, 65.95, 63.88, 63.69, 61.80, 60.22 (C-2ꢀ6),
/
54.93 (CH3). Anal. Calcd for C170H148O46: C, 69.77; H,
5.06. Found: C, 70.01; H, 5.13.
H-1 of Manp), 4.16ꢀ
/
4.07 (m, 3 H), 3.99ꢀ3.46 (m, 32 H),
/
3.30 (m, 1 H), 3.29 (s, 3 H, CH3O); 13C NMR (D2O): d
102.19, 101.58, 100.72, 100.71, 100.69 (5 C-1 of Manp),
99.37 (C-1 of Glcp), 78.82, 78.66, 77.89, 77.69, 77.29,
73.56, 73.39, 73.07, 72.79, 72.64, 72.15, 71.68, 70.46,
70.27, 70.13, 70.04, 69.84, 69.73, 67.18, 67.03, 66.95,
3.12. Methyl 2,3,4,6-tetra-O-benzoyl-a-
mannopyranosyl-(103)-2,4,6-tri-O-benzoyl-a-
mannopyranosyl-(102)-[a- -glucopyranosyl-(10
4,6-di-O-benzoyl-a- -mannopyranosyl-(102)-3,4,6-tri-
O-benzoyl-a- -mannopyranosyl-(102)-3,4,6-tri-O-
benzoyl-a- -mannopyranoside (15)
D-
/
D-
/
D
/
3)]-
D
/
66.78, 66.31, 62.58, 61.17, 61.00, 60.79 (C-2ꢀ
(CH3). MALDI-TOFMS Calcd for C37H64O31 [M]:
1004.3. Found: 1027.4 [MꢁNa].
/6), 54.93
D
/
D
/
To a solution of 14 (0.40 mg, 0.14 mmol) in 1:4 MeOHꢀ
/
EtOAc (40 mL) was added Pd/C (5%, 40 mg). The
reaction mixture was stirred for 3 days at rt in a
hydrogen atmosphere, at the end of which time TLC
indicated that the debenzylation of 14 was complete.
Then the mixture was filtered, and the filtrate was
concentrated under reduced pressure to dryness. Pur-
ification by column chromatography (1:3 petroleum
Acknowledgements
This work was supported by The Chinese Academy of
Sciences (KZCX3-J-08) and by The National Natural
Science Foundation of China (Projects 30070185 and
39970864).