D.V. Yashunsky et al.
12
dd, J5,6a = 6.2, J6a,6b = 12.0, H-6a’), 3.94 (1 H, dd, J5,6a = 2.3, H-6b’), 4.26 (1
H, d, J1,2 = 7.1, H-1’), 5.90 (1 H, s, H-7), 7.42–7.62 (5 Н, m, Ph); δC (150 MHz,
CD3OD): 63.0 (C-6’), 68.7 (C-7), 71.7, 75.0, 78.1, and 78.5 (C-2’, 3’, 4’, 5’), 102.2
(C-1’), 119.6 (C-8), 129.1, 130.3, 131.1, and 135.0 (Ph); HMRS-ESI (positive
mode): m/z 318.0941 [M+Na]+; calcd. for C14H17NNaO6 318.0948.
(R)-[(6-O-β-D-Glucopyranosyl-β-D-glucopyranosyl)oxy](phenyl)ace
tonitrile [(R)-Amygdalin] (3) (20 mg) was obtained in near-quantitative
yield from 19 (43 mg, 0.045 mmol) according to the general procedure B:
crystals; mp 210–211◦C (EtOH); [α]D +29◦ (c 1.0, H2O); δH (600 MHz, D2O):
3.32–3.57 (7 H, m, H-2’, 2”, 3’, 3”, 4’, 4”, 5”), 3.62 (1 H, m, H-5’), 3.74 (1 H, dd,
J5,6a = 5.9, J6a,6b = 12.5, H-6a”), 3.92 (2 H, m, H-6b” and H-6a’), 4.22 (1 H,
dd, J5,6a = 1.7, J6a,6b = 11.9, H-6b’), 4.59 (1 H, d, J1,2 = 7.9, H-1”), 4.62 (1 H,
d, J1,2 = 7.9, H-1’), 5.90 (1 H, s, H-7), 7.52–7.65 (5 Н, m, Ph); δC (150 MHz,
D2O): 62.0 (C-6”), 69.6 (C-6’), 70.3 (C-7), 70.4, 70.9, 74.0, 74.4, 76.6, 75.7, 76.9,
and 77.1 (C-2’, 2”, 3’, 3”, 4’, 4” 5’, 5”), 102.7 (C-1’), 104.1 (C-1”), 119.8 (C-8),
129.0, 130.6, 131.7, and 133.7 (Ph); HMRS-ESI (positive mode): m/z 480.1473
[M+Na]+; calcd. for C20H27NNaO11 480.1476.
(S)-(6-O-β-D-Glucopyranosyl-β-D-glucopyranosyloxy)(phenyl)aceto
nitrile [(S)-Neoamygdalin] (21) (19 mg) was obtained in near-quantitative
yield from 22 (40 mg, 0.042 mmol) according to the general procedure B:
amorphous powder; [α]D –15◦ (c 1.4, H2O); δH (600 MHz, CD3OD): 3.20–4.20
(12 H, m, H-2’, 2”, 3’, 3”, 4’, 4”, 5’, 5”, 6a,b’, 6a,b”), 4.35 (1 H, d, J1,2 = 7.7,
H-1”), 4.61 (1 H, d, J1,2 = 7.7, H-1’), 5.89 (1 H, s, H-7), 7.36–7.56 (5 Н, m, Ph);
δC (150 MHz, CD3OD): 60.9 (C-6”), 67.2 (C-7), 68.5 (C-6’), 69.5, 69.6, 72.7, 73.1,
75.3, 75.7, 75.8, and 75.9 (C-2’, 2”, 3’, 3”, 4’, 4” 5’, 5”), 100.0 and 103.1 (C-1’, 1”),
116.8 (C-8), 127.2, 128.5, 129.4, and 132.5 (Ph); HMRS-ESI (positive mode):
m/z 480.1459 [M+Na]+; calcd. for C20H27NNaO11 480.1476.
(R)-(6-O-β-D-Glucopyranosyl-β-D-glucopyranosyloxy)(phenyl)aceta
mide [(R)-Amygdalin amide] (20). The acyl-protected derivative of man-
delic amide 19 (40 mg, 0.035 mmol) was dissolved in CH2Cl2 (0.5 mL) and
MeOH (1 mL), 1 M sodium methoxide (0.02 mL) was added, and the mixture
was kept at rt for 2 h. The mixture was made neutral with Amberlite IR-120
(H+). The resin was filtered off and thoroughly washed with MeOH, and the
combined filtrates were concentrated. The residue was purified by silica gel
column chromatography (20:5:15:6:4 EtOAc:MeOH:acetone:CH2Cl2:H2O) to
22
provide (R)-amygdalin amide 20 (16 mg, quant.): amorphous powder; [α]D
–97◦ (c 1, H2O); δH (600 MHz, CD3OD): 3.22–3.43 (8 H, m, H-2’, 2”, 3’, 3”, 4’,
4”, 5’, 5”), 3.67 (1 H, dd, J5,6a = 5.3, J6a,6b = 11.9, H-6a”), 3.79 (1 H, dd, J5,6a
=
5.8, J6a,6b = 11.5, H-6a’), 3.88 (1 H, dd, J5,6a = 1.9, H-6b”), 4.13 (1 H, d, J1,2
= 7.7, H-1”), 4.15 (1 H, dd, J5,6a = 1.9, H-6b’), 4.42 (1 H, d, J1,2 = 7.8, H-1’),
5.31 (1 H, s, H-7), 7.32–7.54 (5 Н, m, Ph); δC (150 MHz, CD3OD): 63.0 (C-6”),
70.0 (C-7), 71.8 (C-6’), 71.9, 75.1, 75.4, 77.5, 77.7, 78.2, 78.3, and 80.0 (C-2’,
2”, 3’, 3”, 4’, 4” 5’, 5”), 101.0 and 105.1 (C-1’, 1”), 129.5, 129.7, 129.9, and 133.5