9926
N. Tsutsui et al. / Tetrahedron 69 (2013) 9917e9930
1172, 1092, 1038. 1H NMR (400 MHz, CDCl3)
d
: 1.34/1.37/1.459/1.462
(each dt, J¼16.0, 7.6 Hz, 1H, COCH2(CH2)5CH3), 3.14 (ddd, J¼9.6, 6.4,
[each s, 3H, C(CH3)2], 2.65 (br s, 1H, OH), 3.26 (ddd, J¼9.6, 9.6,
4.8 Hz, 1H, H-50), 3.48 (dd, J¼9.6, 4.8 Hz, 1H, H-6a), 3.56 (dd, J¼9.6,
3.2 Hz, 1H, H-30), 3.58 (dd, J¼9.6, 6.4 Hz, 1H, H-6b), 3.61 (dd, J¼10.4,
7.2 Hz, 1H, H-1a), 3.80 (s, 3H, OCH3), 3.82 (s, 3H, OCH3), 3.83 (dd,
J¼10.0, 9.6 Hz, 1H, H-60a), 3.96 (dd, J¼10.4, 6.4 Hz, 1H, H-1b), 4.05
(d, J¼3.2 Hz, 1H, H-20), 4.08 (dd, J¼9.6, 9.6 Hz, 1H, H-40), 4.22 (dd,
J¼7.2, 5.6 Hz, 1H, H-4), 4.25 (dd, J¼7.2, 6.0 Hz, 1H, H-3), 4.28 (dd,
J¼10.0, 4.8 Hz, 1H, H-60b), 4.33 (ddd, J¼6.4, 5.6, 4.8 Hz, 1H, H-5),
4.46e4.50 (m, 1H, H-2), 4.48/4.56 (each d, J¼11.6 Hz, 1H, OCH2Ph),
4.49 (s, 1H, H-10), 4.68/4.76 (each d, J¼12.0 Hz, 1H, OCH2C6H4OCH3),
5.55 (s, 1H, OCHC6H4OCH3), 6.86 (d, J¼8.4 Hz, 2H, Ar), 6.91 (d,
J¼8.4 Hz, 2H, Ar), 7.28e7.36 (m, 7H, Ar), 7.42 (d, J¼8.4 Hz, 2H, Ar).
2.4 Hz, 1H, H-50), 3.33 (dd, J¼10.0, 4.8 Hz, 1H, H-6a), 3.37 (dd, J¼9.6,
9.6 Hz, 1H, H-40), 3.45 (dd, J¼10.8, 4.4 Hz, 1H, H-1a), 3.50 (dd,
J¼10.0, 7.2 Hz, 1H, H-6b), 3.51 (dd, J¼9.6, 2.8 Hz, 1H, H-30), 3.59 (dd,
J¼12.0, 6.4 Hz, 1H, H-60a), 3.81 (dd, J¼12.0, 2.4 Hz, 1H, H-60b), 3.87
(dd, J¼10.8, 7.2 Hz, 1H, H-1b), 4.15 (ddd, J¼7.2, 4.8, 4.8 Hz, 1H, H-5),
4.16 (dd, J¼5.6, 4.8 Hz, 1H, H-4), 4.26 (dd, J¼6.8, 5.6 Hz, 1H, H-3),
4.31 (ddd, J¼7.2, 6.8, 4.4 Hz, 1H, H-2), 4.39/4.44 (each d, J¼11.6 Hz,
1H, OCH2Ph), 4.53 (s, 1H, H-10), 5.24 (d, J¼2.8 Hz, 1H, H-20),
7.17e7.26 (m, 5H, Ar). 13C NMR (100 MHz, CD3OD)
d: 14.4 (q), 23.7
(t), 25.76 (q), 25.84 (q), 25.9 (t), 28.0 (q, 2C), 30.2 (t, 2C), 32.9 (t),
35.1 (t), 63.1 (t), 68.9 (d), 69.0 (t), 70.3 (t), 72.8 (d), 73.6 (d), 74.4 (t),
76.4 (d), 76.6 (d), 76.65 (d), 76.71 (d), 78.7 (d), 100.2 (d), 109.6 (s),
109.7 (s), 128.9 (d), 129.2 (d, 2C), 129.5 (d, 2C), 139.3 (s), 175.0 (s).
FABMS m/z (%): 663 ([MþNa]þ, 16), 91 (100). FABHRMS calcd for
13C NMR (100 MHz, CDCl3)
d: 25.4 (q, 2C), 27.6 (q), 27.8 (q), 55.2 (q),
55.3 (q), 66.9 (d), 67.9 (t), 68.5 (t), 69.0 (t), 69.7 (d), 72.1 (t), 73.6 (t),
75.1 (d), 75.2 (d), 75.3 (d), 75.5 (d), 76.1 (d), 78.3 (d), 100.1 (d), 101.5
(d), 108.6 (s), 108.8 (s), 113.6 (d, 2C), 113.8 (d, 2C), 127.3 (d, 2C), 127.9
(d),128.1 (d, 2C),128.5 (d, 2C),129.5 (d, 2C),129.9 (s), 130.0 (s), 137.6
(s), 159.3 (s), 160.0 (s). FABMS m/z (%): 775 ([MþNa]þ, 4), 57 (100).
FABHRMS calcd for C41H52O13Na [MþNa]þ: 775.3306; found:
775.3306.
C
33H52O12Na [MþNa]þ: 663.3356; found: 663.3382.
3.1.18. 6-O-Benzyl-2,3:4,5-di-O-isopropylidene-
D-mannitol-1-yl
3,4,6-tri-O-hexanoyl-2-O-octanoyl- -mannopyranoside
b-D
(16). Following the method used for the esterification of 12, 15
(149 mg, 0.233 mmol) was treated with hexanoic anhydride
(0.21 mL, 0.932 mmol). Work-up and column chromatography (n-
3.1.16. 6-O-Benzyl-2,3:4,5-di-O-isopropylidene-
p-methoxybenzyl-4,6-O-p-methoxybenzylidene-2-O-octanoyl-
D
-mannitol-1-yl 3-O-
hexaneeEtOAc, 8/1) gave title compound 16 (188 mg, 87%) as
24
b
-
D
-
a colorless oil. [
a
]
ꢀ20.3 (c 1.02, CHCl3). IR (neat) cmꢀ1: 1748,
D
mannopyranoside (14). Following the method used for the esteri-
fication of 10, 13 (373 mg, 0.496 mmol) was esterified with octanoyl
chloride (0.13 mL, 0.744 mmol). Work-up and column chromatog-
raphy (n-hexaneeEtOAc, 8/1) gave quantitatively title compound
1373, 1246, 1219, 1161, 1099. 1H NMR (400 MHz, CDCl3)
d: 0.88/
0.894 (each t, J¼6.8 Hz, 3H, CH3), 0.885 (t, J¼6.8 Hz, 6H, acyl CH3),
1.23e1.35 (m, 20H, acyl CH2), 1.34/1.35/1.44/1.45 [each s, 3H,
C(CH3)2],1.51e1.66 (m, 8H, acyl CH2), 2.17/2.22/2.23/2.29/2.30/2.34/
2.40/2.45 (each dt, J¼15.6, 7.6 Hz, 1H, COCH2), 3.42 (dd, J¼9.6,
4.8 Hz,1H, H-6a), 3.54 (dd, J¼10.4, 5.2 Hz,1H, H-1a), 3.55 (dd, J¼9.6,
8.4 Hz, 1H, H-6b), 3.57 (ddd, J¼10.0, 5.6, 2.4 Hz, 1H, H-50), 3.91 (dd,
J¼10.4, 7.2 Hz, 1H, H-1b), 4.15 (dd, J¼12.0, 2.4 Hz, 1H, H-60a), 4.212
(dd, J¼12.0, 5.6 Hz, 1H, H-60b), 4.19e4.27 (m, 3H, H-3, H-4 and H-5),
4.37 (ddd, J¼7.6, 5.2, 5.2 Hz, 1H, H-2), 4.46/4.53 (each d, J¼12.0 Hz,
1H, OCH2Ph), 4.64 (d, J¼0.8 Hz, 1H, H-10), 5.02 (dd, J¼10.0, 3.2 Hz,
1H, H-30), 5.24 (dd, J¼10.0, 10.0 Hz, 1H, H-40), 5.49 (dd, J¼3.2, 0.8 Hz,
14 (436 mg) as a colorless oil. [
a
]
D
25 ꢀ34.3 (c 0.98, CHCl3). IR (neat)
cmꢀ1: 1744, 1516, 1373, 1250, 1092, 1045. 1H NMR (400 MHz, CDCl3)
d:
0.86 (t, J¼6.8 Hz, 3H, CO(CH2)6CH3), 1.24e1.32 (m, 8H,
CO(CH2)2(CH2)4CH3), 1.34/1.37/1.44/1.46 [each s, 3H, C(CH3)2], 1.63
(tt, J¼7.2, 7.2 Hz, 2H, COCH2CH2(CH2)4CH3), 2.43 (t, J¼7.2 Hz, 2H,
COCH2(CH2)5CH3), 3.27 (ddd, J¼10.0, 10.0, 4.8 Hz, 1H, H-50), 3.44
(dd, J¼9.6, 4.8 Hz, 1H, H-6a), 3.56 (dd, J¼10.4, 4.8 Hz, 1H, H-1a), 3.57
(dd, J¼9.6, 7.6 Hz, 1H, H-6b), 3.62 (dd, J¼10.0, 3.6 Hz, 1H, H-30), 3.79
(s, 3H, OCH3), 3.82 (s, 3H, OCH3), 3.82 (dd, J¼10.4, 10.0 Hz, 1H, H-60),
3.898 (dd, J¼10.0,10.0 Hz,1H, H-40), 3.900 (dd, J¼10.4, 7.6 Hz,1H, H-
1b), 4.22 (dd, J¼7.6, 5.6 Hz, 1H, H-4), 4.25 (dd, J¼5.6, 5.2 Hz, 1H, H-
3), 4.27 (dd, J¼7.6, 7.6, 4.8 Hz, 1H, H-5), 4.28 (dd, J¼10.4, 4.8 Hz, 1H,
H-60b), 4.37 (ddd, J¼7.6, 5.2, 4.8 Hz, 1H, H-2), 4.48/4.53 (each d,
J¼12.0 Hz, 1H, OCH2Ph), 4.56 (d, J¼0.8 Hz, 1H, H-10), 4.53/4.66 (each
d, J¼12.0 Hz, 1H, OCH2C6H4OCH3), 5.54 (s, 1H, OCHC6H4OCH3), 5.61
(dd, J¼3.6, 0.8 Hz, 1H, H-20), 6.84 (d, J¼8.8 Hz, 2H, Ar), 6.91 (d,
J¼8.8 Hz, 2H, Ar), 7.27e7.36 (m, 7H, Ar), 7.41 (d, J¼8.8 Hz, 2H, Ar).
1H, H-20), 7.27e7.38 (m, 5H, Ar). 13C NMR (100 MHz, CDCl3)
d: 13.80
(q), 13.82 (q), 13.9 (q), 14.0 (q), 22.2 (t, 2C), 22.3 (t), 22.6 (t), 24.2 (t),
24.4 (t), 24.5 (t), 25.0 (t), 25.3 (q), 25.6 (q), 27.7 (q), 27.9 (q), 28.99
(t), 29.02 (t), 31.2 (t, 2C), 31.3 (t), 31.7 (t), 33.93 (t), 33.94 (t), 34.00
(t), 34.02 (t), 62.4 (t), 65.7 (d), 67.8 (t), 68.4 (d), 69.0 (t), 71.0 (d), 72.6
(d), 73.5 (t), 75.0 (d), 75.2 (d, 2C), 75.3 (d), 98.2 (d), 108.6 (s), 108.7
(s), 127.8 (d), 128.0 (d, 2C), 128.5 (d, 2C), 137.7 (s), 172.2 (s), 172.6 (s),
173.0 (s), 173.4 (s). FABMS m/z (%): 957 ([MþNa]þ, 5), 73 (100).
FABHRMS calcd for C51H82O15Na [MþNa]þ: 957.5551; found:
957.5539.
13C NMR (100 MHz, CDCl3)
d: 14.1 (q), 22.6 (t), 24.9 (t), 25.5 (q), 25.6
(q), 27.7 (q), 27.9 (q), 29.0 (t, 2C), 31.7 (t), 34.1 (t), 55.2 (q), 55.3 (q),
67.3 (d), 67.8 (t), 68.3 (d), 68.4 (t), 69.1 (t), 71.2 (t), 73.6 (t), 75.0 (d),
75.16 (d), 75.24 (d, 2C), 75.3 (d), 77.8 (d), 99.2 (d), 101.5 (d),108.6 (s),
108.7 (s), 113.5 (d, 2C), 113.7 (d, 2C), 127.4 (d, 2C), 127.86 (d), 127.94
(d, 2C), 128.5 (d, 2C), 129.4 (d, 2C), 129.76 (s), 129.84 (s), 137.7 (s),
159.3 (s), 160.0 (s), 173.2 (s). FABMS m/z (%): 901 ([MþNa]þ, 9), 121
(100). FABHRMS calcd for C49H66O14Na [MþNa]þ: 901.4350; found:
901.4349.
3.1.19. 2,3:4,5-Di-O-isopropylidene-
D
-mannitol-1-yl 3,4,6-tri-O-hex-
anoyl-2-O-octanoyl- -mannopyranoside
b-D
(17). Following the
method used for the hydrogenation of 11, a solution of 16 (30.0 mg,
0.0321 mmol) in a mixture of acetic acid (0.2 mL) and MeOH
(1.0 mL) was treated with 10% palladium on carbon (5.0 mg) until
uptake of hydrogen ceased. Work-up and column chromatography
(n-hexaneeEtOAc, 5/1) gave title compound 17 (21.1 mg, 78%) as
a colorless oil. [
a]
24 ꢀ27.9 (c 1.02, CHCl3). IR (neat) cmꢀ1: 1748,1377,
D
3.1.17. 6-O-Benzyl-2,3:4,5-di-O-isopropylidene-D-mannitol-1-yl 2-O-
1246, 1219, 1165, 1099. 1H NMR (400 MHz, CDCl3)
d: 0.881/0.883/
octanoyl- -mannopyranoside (15). Following the method
b
-
D
0.89/0.90 (each t, J¼6.8 Hz, 3H, acyl CH3), 1.26e1.38 (m, 20H, acyl
CH2), 1.37/1.38/1.48/1.51 [each s, 3H, C(CH3)2], 1.52e1.67 (m, 8H,
acyl CH2), 2.17/2.22/2.23/2.29/2.31/2.35/2.41/2.46 (each dt, J¼16.0,
7.6 Hz, 1H, COCH2), 3.58 (dd, J¼12.0, 4.8 Hz, 1H, H-6a), 3.63 (dd,
J¼10.0, 4.0 Hz, 1H, H-1a), 3.64 (dd, J¼12.0, 5.6 Hz, 1H, H-6b), 3.66
(ddd, J¼10.0, 5.6, 2.8 Hz, 1H, H-50), 4.01 (dd, J¼10.0, 7.2 Hz, 1H, H-
1b), 4.17 (dd, J¼12.4, 2.8 Hz, 1H, H-60a), 4.216 (ddd, J¼6.0, 5.6,
4.8 Hz, 1H, H-5), 4.223 (dd, J¼12.4, 5.6 Hz, 1H, H-60b), 4.28 (dd,
J¼6.0, 6.0 Hz, 1H, H-3), 4.34 (ddd, J¼7.2, 6.0, 4.0 Hz, 1H, H-2), 4.37
(dd, J¼6.0, 6.0 Hz, 1H, H-4), 4.72 (s, 1H, H-10), 5.05 (dd, J¼10.0,
used for the de-O-p-methoxybenzylation of 8a, 14 (429 mg,
0.488 mmol) was treated with DDQ (231 mg, 0.977 mmol) in
a mixture of CH2Cl2 (4.8 mL) and H2O (0.2 mL). Work-up and col-
umn chromatography (CHCl3eMeOH, 30/1) gave title compound 15
(176 mg, 56%) as a colorless oil. [
a
]
D
24 ꢀ14.5 (c 1.05, CHCl3). IR (neat)
cmꢀ1: 3445, 1744, 1373, 1246, 1219, 1165, 1076. 1H NMR (400 MHz,
CD3OD)
d
: 0.80 (t, J¼7.2 Hz, 3H, CO(CH2)6CH3), 1.14e1.26 (m, 8H,
CO(CH2)2(CH2)4CH3), 1.20/1.26/1.305/1.314 [each s, 3H, C(CH3)2],
1.51 (ddt, J¼7.6, 7.6, 7.6 Hz, 2H, COCH2CH2(CH2)4CH3), 2.27/2.31