H. Ando et al. / Carbohydrate Research 341 (2006) 1522–1532
1531
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21a; [a]D ꢀ12.7 (c 1.6, CHCl3); H NMR (400 MHz,
CDCl3): d 7.56–7.22 (m, 25H, 5Ph), 6.50 (d, 1H, NH),
5.31 (dd, 1H, H-7), 5.18 (d, 1H, J1,2 = 3.3 Hz, H-1Fuc),
5.02–4.94 (m, 2H, H-4Neu and PhCH2), 4.82–4.46 (m,
7H, 4PhCH2), 4.21–4.07 (m, 4H, H-6Neu, H-3Fuc, H-
90Neu, and H-5Fuc), 4.04–3.97 (m, 2H, H-2Fuc and H-
J1,2 = 3.7 Hz, H-1Fuc), 4.95 (d, 1H, PhCH2), 4.86 (m,
1H, H-4Neu), 4.78–4.38 (m, 7H, PhCH2), 4.21 (dd, 1H,
H-6Neu), 4.01–3.96 (m, 2H, H-5Fuc and H-2Fuc), 3.87
(m, 1H, H-5Neu), 3.81 (m, 1H, H-8Neu), 3.73–3.70 (m,
3H, H-3Fuc, H-4Fuc, and H-9Neu), 3.51 (dd, 1H, H-
90Neu), 2.42 (dd, 1H, H-3axNeu), 1.96–1.89 (m, 7H, H-
3eqNeu and 2Ac), 1.08 (d, 1H, H-6Fuc); 13C NMR
(100 MHz, CDCl3): d 170.2, 169.7, 168.5, 138.6, 138.5,
138.3, 137.3, 136.1, 128.9, 128.8, 128.6, 128.5, 128.4,
128.3, 128.2, 128.0, 127.7, 127.7, 127.6, 127.3, 97.4,
85.7, 78.4, 78.1, 75.7, 75.3, 74.8, 73.6, 73.0, 72.8, 72.0,
68.9, 68.5, 67.1, 49.7, 37.8, 29.6, 21.0, 20.9, 16.7; MAL-
DI-TOFMS m/z calcd for C53H57NO12S [M+Na]+:
954.35. Found 954.35. 22b: [a]D +37.4 (c 0.5, CHCl3);
1H NMR (500 MHz, CDCl3): d 7.59–7.10 (m, 25H,
5Ph), 5.74 (m, 2H, NH and H-7Neu), 4.82–4.73 (m,
5H, H-4Neu and 2PhCH2), 4.28 (d, 1H, J1,2 = 7.6 Hz,
H-1Fuc), 4.26 (m, 1H, H-8Neu), 3.89 (dd, 1H, H-6Neu),
3.83–3.71 (m, 4H, H-9Neu, H-90Neu, H-5Neu, and
H-2Fuc), 3.55 (m, 1H, H-4Fuc), 3.43–3.39 (m, 2H,
H-3Fuc, H-5Fuc), 2.39 (near t, 1H, Jgem = 14.6 Hz,
J3eq,4 = 10.4 Hz, H-3eqNeu), 2.07 and 157 (2s, 6H,
8
Neu), 3.81 (q, 1H, H-5Neu), 3.68 (d, 1H, H-4Fuc), 3.59–
3.54 (m, 4H, H-9Neu and Me), 2.78 (dd, 1H, H-3eqNeu),
2.05–1.85 (m, 7H, H-3ax Neu, 2Ac), 1.09 (d, 1H,
J5,6 = 6.6 Hz, H-6Fuc); 13C NMR (125 MHz, CDCl3): d
170.9, 170.6, 169.7, 168.6, 139.3, 139.0, 138.3, 138.2,
137.1, 130.2, 129.0, 128.8, 128.6, 128.5, 128.5, 128.4,
128.3, 128.2, 128.0, 127.8, 127.7, 127.6, 127.5, 95.0,
86.9, 79.0, 78.1, 76.4, 75.2, 73.8, 73.5, 73.1, 73.0, 72.6,
69.8, 69.6, 67.1, 66.9, 53.0, 50.5, 38.1, 29.9, 21.0, 20.8,
17.1; MALDI-TOFMS m/z calcd for C56H60F3NO14S
[M+Na]+: 1082.36. Found 1082.38.
3.19. Phenyl 4,7-di-O-acetyl-5-amino-9-O-benzyl-3,5-
dideoxy-2-thio-8-O-(2,3,4-tri-O-benzyl-a-L-fucopyran-
osyl)-D-glycero-a-D-galacto-2-nonulopyranoside-1,5-
lactam (22)
2Ac), 1.98 (dd, 1H, H-3axNeu), 1.12 (d, 3H, J5,6
=
With fucosyl fluoride donor 14: To a solution of com-
pound 12 (100 mg, 0.19 mmol) and compound 14
(100 mg, 0.23 mmol) in CH2Cl2 (5.3 mL), 4 A molecular
6.6 Hz, H-6Fuc); 13C NMR (100 MHz, CDCl3); d
170.5, 169.4, 168.7, 138.8, 138.2, 138.1, 137.7, 136.1,
128.9, 128.8, 128.8, 128.6, 128.4, 128.4, 128.4, 128.2,
128.2, 128.1, 128.0, 127.7, 127.6, 127.6, 127.5, 127.3,
105.6, 105.5, 85.7, 82.8, 79.1, 78.4, 78.2, 78.1, 78.0,
75.2, 74.7, 74.4, 73.5, 73.2, 73.2, 73.1, 72.7, 70.4, 69.3,
69.0, 49.6, 49.5, 49.5, 37.6, 29.6, 21.3, 21.3, 21.2, 20.4,
20.3, 16.8; MALDI-TOFMS m/z calcd for C53H57-
NO12S [M+Na]+: 954.35. Found 954.33.
˚
sieves (240 mg) was added. The suspension was stirred
for 1 h and cooled to ꢀ80 °C. To the mixture, Cp2ZrCl2
(81 mg, 0.28 mmol) and AgOTf (71 mg, 0.28 mmol)
were added, and stirring was continued for 44 h until
TLC analysis (2:1, n-Hex/EtOAc) indicated the comple-
tion of the reaction. The reaction mixture was filtered
through Celite. The combined filtrate and washings were
extracted with CHCl3, and the organic layer was washed
with satd aq NaHCO3 and water, dried over Na2SO4,
and concentrated. The residue was purified with column
chromatography on silica gel (2:1, n-Hex/EtOAc) to give
22a (115 mg, 65%) and the corresponding b-isomer 22b
(38 mg, 21%).
3.20. Phenyl 4,7-di-O-acetyl-9-O-benzyl-5-benzyloxy-
carbamoyl-3,5-dideoxy-2-thio-8-O-(2,3,4-tri-O-benzyl-
a-L-fucopyranosyl)-D-glycero-a-D-galacto-2-nonulo-
pyranoside-1,5-lactam (23)
To a solution of compound 22 (207 mg, 0.22 mmol) in
pyridine (2.2 mL), CbzOSu (166 mg, 0.68 mmol) was
added under an argon atmosphere. The suspension
was stirred for 18 h at rt (TLC; 3:1, PhMe/EtOAc).
After the quenching by the addition of CH3OH, the
mixture was co-evaporated with toluene. The residue
was dissolved in CHCl3, washed with 2 M HCl, water,
satd aq NaHCO3 and brine, dried (Na2SO4), and con-
centrated. The residue was purified by chromatography
on silica gel (15:1, toluene/EtOAc) to give 23 (217 mg,
With phenylthioglycoside donor 15: To a solution of
compound 12 (100 mg, 0.19 mmol) and compound 15
˚
(153 mg, 0.29 mmol) in toluene (2.0 mL) 4 A molecular
sieves (240 mg) was added. The suspension was stirred
for 1 h and cooled to ꢀ20 °C. To the mixture, NIS
(79 mg, 0.35 mmol) and TfOH (3.1 lL, 35 lmol) were
added and stirring was continued for 2.5 h. The reaction
mixture was alkalized to pH 8 with satd aq NaHCO3 at
0 °C and filtered through Celite. The combined filtrate
and washings were extracted with CHCl3, and the or-
ganic layer was washed with satd Na2S2O3 and brine,
dried over Na2SO4, and concentrated. The residue was
purified with column chromatography on silica gel
(2:1, n-Hex/EtOAc) to afford 22a (133 mg, 74%) and
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92%): [a]D +2.0 (c 1.0, CHCl3); H NMR (500 MHz,
CDCl3): d 7.56–7.15 (m, 30H, 6Ph), 5.66 (dd, 1H,
J6,7 = 4.8 Hz, J7,8 = 9.0 Hz, H-7Neu), 5.25 and 5.21
(2d, 2H, Jgem = 12.4 Hz, PhCH2), 5.08 (m, 1H, H-
5Neu), 5.01 (d, 1H, J1,2 = 3.6 Hz, H-1Fuc), 4.98 (m, 1H,
J3eq,4 = 10.4 Hz, J3ax,4 = 5.8 Hz, H-4Neu), 4.93–4.32
(m, 8H, PhCH2), 4.30 (near dd, 1H, H-6Neu), 3.94 (dd,
1H, J2,3 = 10.2 Hz, H-2Fuc), 3.88 (m, 2H, H-8Neu and
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22b (31 mg, 17%). 22a: [a]D ꢀ30.6 (c 0.5, CHCl3); H
NMR (400 MHz, CDCl3): d 7.52–7.24 (m, 25H, 5Ph),
6.74 (m, 1H, NH), 5.60 (dd, 1H, H-7Neu), 5.05 (d, 1H,