(m, H-23), 1.82 (m, H-16), 1.75 (m, H-1), 1.74 (2H, m, H-23 and
H-22), 1.74 (m, H-22), 1.68 (m, H-7), 1.66 (2H, m, H-6 and H-11),
1.61 (m, H-16), 1.58 (m, H-15), 1.55 (m, H-12), 1.52 (m, H-3),
1.50 (2H, m, H-2 and H-6), 1.48 (m, H-22), 1.47 (m, H-9), 1.448
(3H, s, H-27), 1.38 (2H, m, H-2 and H-7), 1.30 (m, H-3), 1.276
(3H, s, H-26), 1.273 (3H, s, H-21), 1.22(m, H-15), 1.20 (m, H-11),
1.151(3H, s, H-30), 1.15 (3H, s, H-18), 1.039 (3H, s, H-28), 1.01
(3H, s, H-19), 0.998 (3H, s, H-29), 0.919 (br d, J 12.5, H-5), 0.87
(m, H-1). The assignments of H-2 and H-6 and those of H-26 and
H-27 are exchangeable. 13C NMR (C6D6, 150.9 MHz), d 85.31 (s,
C-20), 83.98 (d, C-24), 71.28 (s, C-25), 57.29 (d, C-5), 51.15 (d,
C-9), 49.43 (s, C-14), 48.66 (d, C-17), 43.81 (2C, t for C-3 and d for
C-13), 41.17 (s, C-8), 40.81 (t, C-1), 38.22 (t, C-22), 37.69 (s, C-10),
35.63 (t, C-7), 33.63 (q, C-28), 33.54 (s, C-4), 32.72 (t, C-15), 27.78
(q, C-27), 27.08 (t, C-16), 26.21 (t, C-12), 25.79 (t, C-23), 25.29 (q,
C-26), 25.23 (q, C-21), 22.65 (t, C-11), 21.76 (q, C-29), 19.12 (t,
C-2), 19.08 (t, C-6), 17.20 (q, C-30), 16.47 (q, C-19), 16.13 (q, C-
18). The assignments of C-2 and C-6 and those of C-26 and C-27
are exchangeable. EI-MS m/z (%): 69 (10), 81 (11), 95 (11), 125
(15), 143 (100), 191 (10), 385 (10), 429 (3, M+ − Me). HR-EI-MS:
m/z (M+ − Me), calcd. for C29H49O2, 429.3733; found, 429.3730.
[a]2D5 = −72.5 (c 0.090, EtOH).
Experimental
Please see the ESI for additional experimental data.†
NMR and EI-MS spectroscopic data of enzymatic products 31–42
Products 33, 34, 37 and 38 were measured in both C6D6 and
acetone-d6. NMR data of 39–42-monoacetates were acquired in
both CDCl3 and acetone-d6.
1
Product 31. Oil. H NMR (C6D6, 600.13 MHz), d 5.46 (2H,
br s, H-17 and H-13), 5.10 (br s, H-26), 4.84 (br s, H-26), 3.35 (dd,
10.4, J 1.8, H-21), 2.52 (m, H-7), 2.45 (m, H-12), 2.44 (m, H-19),
2.34 (2H, dt, J 7.6, 7.6, H-16), 2.26 (2H, t, J 7.8, H-15), 2.21 (m,
H-19), 2.15 (m, H-12), 2.11 (m, H-7), 1.83 (m, H-1), 1.78 (m, H-9),
1.770 (3H, s, H-27), 1.75 (m, H-6), 1.725 (3H, s, H-28), 1.69 (m,
H-11), 1.66 (m, H-2), 1.62 (m, H-11), 1.61 (m, H-20), 1.55 (m,
H-2), 1.50 (m, H-20), 1.49 (m, H-3), 1.41 (m, H-6), 1.27 (m, H-3),
1.154 (3H, s, H-30), 1.148 (3H, s, H-29), 1.14 (m, H-5), 1.08 (m,
H-1), 0.965 (3H, s, H-23), 0.921 (3H, s, H-24), 0.868 (3H, s, H-25).
13C NMR (C6D6, 150.9 MHz), d 148.87 (s, C-8), 135.29 (s, C-18),
134.95 (s, C-14), 125.80 (d, C-13), 125.13 (d, C-17), 106.66 (t, C-
26), 78.28 (d, C-21), 72.56 (s, C-22), 56.52 (d, C-9), 55.65 (d, C-5),
42.43 (t, C-3), 40.21 (t, C-15), 39.31 (t, C-1), 39.84 (s, C-10), 38.73
(t, C-7), 37.24 (t, C-19), 33.66 (s, C-4), 33.72 (q, C-23), 30.13 (t,
C-20), 27.43 (t, C-12), 27.13 (t, C-16), 26.40 (q, C-29), 24.76 (t, C-
6), 24.24 (t, C-11), 23.58 (q, C-30), 21.89 (q, C-24), 19.76 (t, C-2),
16.16 (q, C-27), 16.06 (q, C-28), 14.75 (q, C-25). The assignments
of H-29, H-30, C-29 and C-30 are exchangeable. EI-MS m/z (%):
69 (50), 81 (100), 95 (53), 109 (40), 135 (34), 137 (42), 153 (30),
189 (13), 191 (23), 411 (11), 426 (10), 444 (5, M+). HR-EI-MS:
Product 34. Solid. 1H NMR (acetone-d6, 600.13 MHz) d 3.78
(very broad d, J 4.4, OH), 3.28 (ddd, J 11.5, 4.4, 4.4, H-24), 2.04
(m, H-13), 2.02 (m, H-12), 1.93 (ddd, J 9.3, 8.5, 7.8, H-17), 1.78
(m, eq, H-23), 1.68 (m, H-22 ax), 1.64 (m, H-1), 1.62 (m, H-2), 1.60
(m, H-23 ax), 1.59 (2H, m, H-7 and H-16), 1.56 (2H, m, H-11 and
H-12), 1.51 (m, H-6), 1.44(m, H-9), 1.41 (m, H-2), 1.40 (m, H-16),
1.39 (m, H-6), 1.38 (m, H-15), 1.35(m, H-3), 1.32 (m, H-22eq.),
1.284 (3H, s, H-21), 1.23 (m, H-7), 1.179 (3H, s, H-27), 1.17 (m,
H-11), 1.151 (3H, s, H-26), 1.15 (m, H-3), 1.034 (3H, s, H-30),
1.03(m, H-15), 0.946 (3H, s, H-18), 0.87 (m, H-1), 0.853 (3H, s,
m/z (M+), calcd. for C30H52O2, 444.3967; found, 444.3972. [a]D25
+79.6 (c 0.40, EtOH).
=
1
Product 32. Oil. H NMR (C6D6, 600.13 MHz), d 5.58 (br s,
H-7), 5.46 (br t, J 6.8, H-17), 5.45 (br t, J 6.8, H-13), 3.34 (br d,
J 9.5, H-21), 2.45 (m, H-19), 2.42 (m, H-12), 2.34 (2H, m, H-16),
2.25 (2H, t, J 7.4), 2.21 (2H, m, H-19 and H-12), 2.06 (m, H-6),
1.99 (m, H-6), 1.98 (m, H-1), 1.916 (3H, s, H-26), 1.79 (m, H-9),
1.773 (3H, s, H-27), 1.731 (3H, s, H-28), 1.65 (2H, m, H-2 and H-
11), 1.61 (m, H-20), 1.55 (m, H-2), 1.51 (m, H-3), 1.50 (m, H-20),
1.44 (m, H-11), 1.32 (dd, J 11.9, 4.9, H-5), 1.27 (ddd, J 14,13.9,
3.9, H-3), 1.150 (3H, s, H-30), 1.145 (3H, s, H-29), 1.08 (m, H-1),
1.000 (3H, s, H-24), 0.980 (3H, s, H-23), 0.955 (3H, s, H-25). The
assignments of H-29 and H-3 are exchangeable. 13C NMR (C6D6,
150.9 MHz), d 135.39 (s, C-8), 135.34 (s, C-18), 134.89 (s, C-14),
125.52 (d, C-13), 125.07 (d, C-17), 122.54 (d, C-7), 78.28 (t, C-21),
72.54 (s, C-22), 54.57 (d, C-9), 50.37 (d, C-5), 42.64 (t, C-3), 40.17
(t, C-15), 39.49 (t, C-1), 37.23 (t, C-19), 37.02 (s, C-10), 33.35 (q,
C-23), 33.08 (s, C-4), 30.76 (t, C-12), 30.14 (t, C-20), 27.74 (t, C-
11), 27.09 (t, C-16), 26.39 (q, C-29), 24.20 (t, C-6), 23.58 (q, C-30),
22.46 (q, C-26), 22.03 (q, C-24), 19.21 (t, C-2), 16.24 (q, C-27),
16.06 (q, C-28), 13.77 (q, C-25). The assignments of C-8 and C-18
and those of C-29 and C-30 are exchangeable. EI-MS m/z (%): 69
(50), 81 (100), 95 (53), 109 (58), 135 (34), 153 (42), 189 (42), 191
(54), 204 (38), 411 (6), 426 (7), 444 (5, M+). HR-EI-MS: m/z (M+),
calcd. for C30H52O2, 444.3967; found, 444.3966. [a]2D5 = −33.3 (c
0.41, EtOH).
H-19), 0.845 (3H, s, H-28), 0.82(m, H-5), 0.813(3H, s, H-29). 13
C
NMR (acetone-d6, 150.9 MHz), d 75.83 (2C, s, C-20 and C-25),
75.36 (d, C-24), 57.80 (d, C-5), 51.62 (d, C-9), 51.41 (d, C-17),
49.74 (s, C-14), 44.83 (d, C-13), 42.89 (t, C-3), 41.61 (s, C-8), 41.33
(t, C-1), 38.14 (s, C-10), 36.07 (t, C-7), 35.05 (t, C-22), 33.93 (s,
C-4), 33.75 (q, C-28), 33.11 (t, C-15), 30.49 (q, C-27), 27.71 (t,
C-16), 27.53 (q, C-21), 26.95 (t, C-12), 25.89 (t, C-23), 23.22 (t, C-
11), 22.49 (q, C-26), 21.83 (q, C-29), 19.21 (t, C-2), 19.12 (t, C-6),
17.29 (q, C-30), 16.61 (q, C-19), 16.28 (q, C-18). The assignments
of C-2 and C-6 are exchangeable. 1H NMR (C6D6, 600.13 MHz)
d 3.22 (dd, J 11.5, 4.4, H-24), 2.18(m, H-12), 2.14 (m, H-13), 1.91
(m, H-17), 1.78 (3H, m, H-1, H-6 and H-7), 1.77 (m, H-12), 1.75
(m, H-2), 1.74 (2H, m, H-11 and H-16), 1.68 (2H, m, H-22 and
H-23eq), 1.66 (m, H-16), 1.62 (m, H-9), 1.58 (m, H-14), 1.55 (m,
H-6), 1.52 (m, H-3), 1.50 (m, H-2), 1.46 (m, H-23ax), 1.44 (m,
H-7), 1.419 (3H, s, H-27), 1.35 (m, H-11), 1.336 (3H, s, H-21),
1.32 (3H, s, H-26), 1.30 (m, H-14), 1.29 (3H, s, H-30), 1.28 (m,
H-3), 1.22 (m, H-22), 1.123 (3H, s, H-18), 1.03 (6H, s, H-19 and
H-28), 1.004 (3H, s, H-29), 0.973 (dd, J 12.0, 2.4, H-5), 0.94 (m,
H-1). The assignments of H-2 and H-6 in C6D6 are exchangeable.
13C NMR (C6D6, 150.9 MHz) d 13C NMR (C6D6, 150.9 MHz), d
75.32 (s for C-20, d for C-24), 75.07 (s, C-25), 57.42 (d, C-5), 51.86
(d, C-17), 51.17 (d, C-9), 49.38 (s, C-14), 44.33 (d, C-13), 42.54 (t,
C-3), 41.23 (s, C-8), 40.89 (t, C-1), 37.74 (s, C-10), 35.78 (t, C-7),
34.63 (t, C-22), 33.65 (q, C-28), 33.56 (s, C-4), 32.84 (t, C-15), 30.11
(q, C-27), 27.49 (t, C-16), 27.25 (q, C-21), 26.58 (t, C-12), 25.57
1
Product 33. Oil. H NMR (C6D6, 600.13 MHz), d 3.74 (t, J
7.3, H-24), 2.16 (m, H-17), 2.07 (m, H-13), 1.93 (m, H-12), 1.91
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Org. Biomol. Chem., 2007, 5, 792–801 | 799
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