(3S,9S )-3-O-Glucoside pentaacetate 48. [α]2D0 Ϫ58.3 (c. 1.05,
᎐ ᎐
dd, J 9.5 and 8, 2Ј-H), 3.29 (1H, ddd, J 9.5, 5.5 and 2, 5Ј-H),
MeOH); νmax/cmϪ1: 3591 and 3508 (OH), 1960 (C᎐C᎐C), 1754
3.32 (1H, t, J 9.5, 4Ј-H), 3.40 (1H, t, J 9.5, 3Ј-H), 3.64 (1H, dd,
J 12.5 and 5.5, 6Ј-H), 3.84 (1H, dd, J 12.5 and 2, 6Ј-H), 4.16
(1H, tt, J 12 and 4, 3-H), 4.49 (1H, dq, J 8 and 6.5, 9-H), 4.59
(1H, d, J 8, 1Ј-H), 5.23 (1H, d, J 8, 8-H); δC(125 MHz, D2O)
21.09 (9-CH3), 28.24 (1-CH3), 30.49 (5-CH3), 31.93 (1-CH3),
34.61 (C1), 47.39 (C4), 47.75 (C2), 60.91 (C6Ј), 64.07 (C3),
69.74 (C4Ј), 72.01 (C5), 73.18 (C2Ј), 74.18 (C9), 76.05
(C3Ј), 76.30 (C5Ј), 95.84 (C8), 99.21 (C1Ј), 115.15 (C6), 200.57
(C7); m/z (SIMS) 411.1978 (Mϩ ϩ Na, C19H32O8Na requires
411.1993).
(COO); δH(500 MHz) 1.06 and 1.29 (each 3H, s, gem-Me), 1.30
(3H, d, J 6.5, 9-Me), 1.33 (1H, dd, J 13.5 and 11, 4-Hax), 1.36
(3H, s, 5-Me), 1.39 (1H, t, J 12, 2-Hax), 1.99 (1H, ddd, J 12, 4.5
and 2.5, 2-Heq), 2.00 (3H), 2.03 (6H), 2.05 (3H) and 2.08 (3H)
(each s, AcO × 5), 2.17 (1H, ddd, J 13.5, 4.5 and 2.5, 4-Heq),
3.72 (1H, ddd, J 10, 5.5 and 2.5, 5Ј-H), 4.13 (1H, dd, J 12.5 and
2.5, 6Ј-H), 4.20 (1H, m, 3-H), 4.25 (1H, dd, J 12.5 and 5.5,
6Ј-H), 4.63 (1H, d, J 8, 1Ј-H), 4.95 (1H, dd, J 10 and 8, 2Ј-H),
5.06 (1H, t, J 10, 4Ј-H), 5.20 (1H, t, J 10, 3Ј-H), 5.35 (2H, m,
8-H and 9-H); δC(125 MHz) 19.85 (9-CH3), 20.62, 20.63, 20.71,
20.76 and 21.27 (CH3COO × 5), 29.37 (1-CH3), 31.08 (5-CH3),
32.05 (1-CH3), 35.05 (C1), 45.44 (C4), 47.06 (C2), 62.27 (C6Ј),
68.37 (C9), 68.66 (C4Ј), 71.52 (C2Ј), 71.73 (C5Ј), 72.28 (C5),
72.94 (C3Ј), 73.40 (C3), 96.14 (C8), 100.01 (C1Ј), 117.43 (C6),
169.27, 169.45, 170.30, 170.33 and 170.65 (CH3COO × 5),
199.26 (C7); m/z (SIMS) 621.2508 (Mϩ ϩ Na, C29H42O13Na
requires 621.2520).
(3S,9R)-9-O-Glucoside 12. [α]2D3 0 (c. 0.77, MeOH); δH(500
MHz, CD3OD) 1.10 and 1.30 (each 3H, s, gem-Me), 1.24 (1H, t,
J 12, 2-Hax), 1.30 (3H, d, J 6.5, 9-Me), 1.31 (1H, 4-Hax), 1.34
(3H, s, 5-Me), 1.85 (1H, ddd, J 12, 4 and 2, 2-Heq), 2.14 (1H,
ddd, J 12.5, 4 and 2, 4-Heq), 3.16 (1H, dd, J 9 and 8, 2Ј-H), 3.23
(1H, ddd, J 9.5, 5.5 and 2.5, 5Ј-H), 3.31 (2H, m, 3Ј-H and 4Ј-H),
3.67 (1H, dd, J 12 and 5.5, 6Ј-H), 3.84 (1H, dd, J 12 and 2.5,
6Ј-H), 4.16 (1H, tt-like, J 11.5 and 4, 3-H), 4.39 (1H, d, J 8,
1Ј-H), 4.40 (1H, quint., J 6.5, 9-H), 5.47 (1H, d, J 6.5, 8-H);
δC(125 MHz, CD3OD) 19.89 (9-CH3), 28.82 (1-CH3), 30.84
(5-CH3), 32.29 (1-CH3), 35.53 (C1), 49.27 (C4), 49.83 (C2),
62.05 (C6Ј), 64.05 (C3), 70.86 (C4Ј), 72.09 (C5), 74.51 (C2Ј),
75.20 (C9), 77.24 (C5Ј), 77.46 (C3Ј), 98.32 (C8), 102.36 (C1Ј),
116.59 (C6), 199.43 (C7); δH(500 MHz, D2O) 1.07 and 1.20
(each 3H, s, gem-Me), 1.25 (1H, t, J 12, 2-Hax), 1.28 (3H, d,
J 6.5, 9-Me), 1.32 (3H, s, 5-Me), 1.38 (1H, dd, J 12.5 and 12,
4-Hax), 1.85 (1H, ddd, J 12, 4 and 2, 2-Heq), 2.11 (1H,
ddd, J 12.5, 4 and 2, 4-Heq), 3.19 (1H, dd, J 9 and 8, 2Ј-H),
3.34 (2H, m, 4Ј-H and 5Ј-H), 3.41 (1H, t, J 9, 3Ј-H), 3.67
(1H, dd, J 12 and 5, 6Ј-H), 3.84 (1H, dd, J 12 and 0.5, 6Ј-H),
4.16 (1H, tt, J 12 and 4, 3-H), 4.44 (1H, quint., J 6.5, 9-H), 4.52
(1H, d, J 8, 1Ј-H), 5.41 (1H, d, J 6.5, 8-H); δC(125 MHz, D2O)
19.83 (9-CH3), 28.33 (1-CH3), 30.38 (5-CH3), 31.66 (1-CH3),
34.70 (C1), 47.42 (C4), 47.91 (C2), 60.90 (C6Ј), 64.10 (C3),
69.69 (C4Ј), 72.23 (C5), 73.41 (C2Ј), 76.04, 76.21 and 76.40
(C3Ј, C5Ј and C9), 96.93 (C8), 101.12 (C1Ј), 115.55 (C6), 199.76
(C7); m/z (SIMS) 411.1996 (Mϩ ϩ Na, C19H32O8Na requires
411.1993).
(3S,9R)-3-O-Glucoside pentaacetate 51. [α]2D0 ϩ25.3 (c. 1.03,
᎐ ᎐
MeOH); νmax/cmϪ1 3593 and 3487 (OH), 1958 (C᎐C᎐C), 1754
(COO); δH(500 MHz) 1.06 and 1.29 (each 3H, s, gem-Me), 1.30
(3H, d, J 6.5, 9-Me), 1.31 (1H, 4-Hax), 1.36 (3H, s, 5-Me), 1.38
(1H, t, J 12, 2-Hax), 2.00, 2.02, 2.03, 2.05 and 2.08 (each 3H,
s, AcO × 5), 2.00 (1H, 2-Heq), 2.18 (1H, ddd, J 12.5, 3.5 and 2,
4-Heq), 3.72 (1H, ddd, J 9.5, 5.5 and 2.5, 5Ј-H), 4.13 (1H, dd,
J 12 and 2.5, 6Ј-H), 4.20 (1H, m, 3-H), 4.25 (1H, dd, J 12 and
5.5, 6Ј-H), 4.64 (1H, d, J 8, 1Ј-H), 4.95 (1H, dd, J 9.5 and 8,
2Ј-H), 5.06 (1H, t, J 9.5, 4Ј-H), 5.20 (1H, t, J 9.5, 3Ј-H), 5.37
(2H, m, 8-H and 9-H); δC(125 MHz) 19.78 (9-CH3), 20.62,
20.64, 20.71, 20.76 and 21.26 (CH3COO × 5), 29.33 (1-CH3),
31.13 (5-CH3), 31.89 (1-CH3), 35.16 (C1), 45.52 (C4), 47.16
(C2), 62.27 (C6Ј), 68.08 (C9), 68.65 (C4Ј), 71.53 (C2Ј), 71.73
(C5Ј), 72.30 (C5), 72.94 (C3Ј), 73.49 (C3), 96.16 (C8), 100.07
(C1Ј), 117.60 (C6), 169.29, 169.47, 170.30, 170.32 and 170.67
(CH3COO × 5), 199.05 (C7); m/z (SIMS) 621.2541 (MϪϩNa,
C29H42O13Na requires 621.2520).
Methanolysis of pentaacetates 42, 45, 48 and 51; typical
procedure
(3S,9S )-3-O-Glucoside 13. [α]2D0 Ϫ57.8 (c. 0.69, MeOH);
δH(500 MHz, D2O) 1.05 and 1.21 (each 3H, s, gem-Me), 1.23
(3H, d, J 6, 9-Me), 1.32 (3H, s, 5-Me), 1.37 (1H, t, J 12, 2-Hax),
1.42 (1H, t, J 12.5, 4-Hax), 1.97 (1H, br d, J 12, 2-Heq), 2.23 (1H,
br d, J 12.5, 4-Heq), 3.18 (1H, dd, J 9 and 8, 2Ј-H), 3.34 (1H, t,
J 9, 4Ј-H), 3.42 (1H, ddd, J 9, 6 and 2, 5Ј-H), 3.45 (1H, t, J 9,
3Ј-H), 3.67 (1H, dd, J 12 and 6, 6Ј-H), 3.87 (1H, dd, J 12 and 2,
6Ј-H), 4.28 (1H, m, 3-H), 4.34 (1H, quint., J 6, 9-H), 4.55 (1H,
d, J 8, 1Ј-H), 5.37 (1H, d, J 6, 8-H); δC(125 MHz, D2O) 21.81
(9-CH3), 28.38 (1-CH3), 30.08 (5-CH3), 31.84 (1-CH3), 34.54
(C1), 44.89 (C4), 46.46 (C2), 60.86 (C6Ј), 66.11 (C9), 69.81
(C4Ј), 72.06 (C5), 73.25 (C2Ј), 73.42 (C3), 75.96 and 76.01
(C3Ј and C5Ј), 98.51 (C8), 100.86 (C1Ј), 115.71 (C6), 199.00
(C7); m/z (SIMS) 411.2007 (Mϩ ϩ Na, C19H32O8Na requires
411.1993).
To a solution of the pentaacetate 42 (101 mg, 0.17 mmol)
in MeOH (5 ml) was added NaOMe (1 M in MeOH; 0.25 ml,
0.25 mmol) and the mixture was stirred at rt for 4 h. The mix-
ture was concentrated to give a residue, which was purified by
SPE CC (CH2Cl2–MeOH, 4:1) to yield the hexaol 11 (59 mg,
1
90%) as a colourless foam. H and 13C NMR data (in CD3OD
solution) of the synthetic (3S,9S)-9-O-glucosides 12 were
identical with those of the glucoside isolated8 from Premna
subscandes, while those (in D2O solution) of 9-O-glucosides 11
and 12 were accordance with those of glucosides previously
prepared.9
(3S,9S )-9-O-Glucoside 11. [α]2D7 Ϫ29.1 (c. 1.00, MeOH);
δH(500 MHz, CD3OD) 1.05 and 1.30 (each 3H, s, gem-Me), 1.23
(1H, t, J 12, 2-Hax), 1.32 (3H, d, J 6.5, 9-Me), 1.30 (1H, 4-Hax),
1.39 (3H, s, 5-Me), 1.84 (1H, ddd, J 12.5, 4.5 and 2, 2-Heq), 2.14
(1H, ddd, J 13, 4.5 and 2, 4-Heq), 3.16 (1H, ddd, J 9, 6 and 2.5,
5Ј-H), 3.18 (1H, br t, J 8, 2Ј-H), 3.30 (2H, m, 3Ј-H and 4Ј-H),
3.65 (1H, dd, J 12 and 6, 6Ј-H), 3.83 (1H, dd, J 12 and 2.5,
6Ј-H), 4.16 (1H, tt-like, J 11.5 and 4.5, 3-H), 4.48 (1H, m, 9-H),
4.50 (1H, d, J 8, 1Ј-H), 5.21 (1H, d, J 8, 8-H); δC(125 MHz,
CD3OD) 22.56 (9-CH3), 29.60 (1-CH3), 31.79 (5-CH3), 33.29
(1-CH3), 36.17 (C1), 49.95 (C4), 50.34 (C2), 62.78 (C6Ј), 64.76
(C3), 71.65 (C4Ј), 72.70 (C5), 74.01 (C9), 75.08 (C2Ј), 78.08
(C5Ј), 78.26 (C3Ј), 97.79 (C8), 101.09 (C1Ј), 116.83 (C6), 201.15
(C7); δH(500 MHz, D2O) 1.03 and 1.20 (each 3H, s, gem-Me),
1.24 (1H, t, J 12, 2-Hax), 1.31 (3H, d, J 6.5, 9-Me), 1.36 (3H, s,
5-Me), 1.36 (1H, dd, J 13.5 and 12, 4-Hax), 1.84 (1H, ddd, J 12,
4 and 2, 2-Heq), 2.11 (1H, ddd, J 13.5, 4 and 2, 4-Heq), 3.22 (1H,
(3S,9R)-3-O-Glucoside 14. [α]2D7 Ϫ26.3 (c. 0.99, MeOH);
δH(500 MHz, D2O) 1.05 and 1.21 (each 3H, s, gem-Me), 1.23
(3H, d, J 6.5, 9-Me), 1.33 (3H, s, 5-Me), 1.37 (1H, t, J 12.5,
2-Hax), 1.43 (1H, dd, J 13 and 12, 4-Hax), 1.96 (1H, ddd, J 12.5,
4 and 2, 2-Heq), 2.24 (1H, ddd, J 13, 4 and 2, 4-Heq), 3.18 (1H,
dd, J 9.5 and 8, 2Ј-H), 3.34 (1H, t, J 9.5, 4Ј-H), 3.43 (1H, ddd,
J 9.5, 6 and 2, 5Ј-H), 3.45 (1H, t, J 9.5, 3Ј-H), 3.67 (1H, dd, J 12
and 6 Hz, 6Ј-H), 3.87 (1H, dd, J 12 and 2, 6Ј-H), 4.29 (1H, m,
3-H), 4.34 (1H, quint, J 6.5, 9-H), 4.56 (1H, d, J 8, 1Ј-H), 5.37
(1H, d, J 6.5, 8-H); δC(125 MHz, D2O) 21.83 (9-CH3), 28.38
(1-CH3), 30.25 (5-CH3), 31.59 (1-CH3), 34.67 (C1), 44.83 (C4),
46.52 (C2), 60.86 (C6Ј), 66.24 (C9), 69.81 (C4Ј), 72.08 (C5),
73.26 (C2Ј), 73.43 (C3), 75.96 and 76.01 (C3Ј and C5Ј), 98.52
J. Chem. Soc., Perkin Trans. 1, 2002, 2833–2844
2843