NETO ET AL.
5
(
1H, m, H‐7a), 2.10 (2H, m, H‐2″), 2.14 (1H, m, H‐2), 2.30 (2H, m, H‐
′), 2.55 (1H, dd, J = 2.9, 10.2 Hz, H‐4), 2.87 (1H, dd, J = 9.1, 11.9 Hz,
H‐1α), 4.69 (1H, s, H‐17a), 4.90 (1H, s, H‐17b), 5.34 (1H, s, H‐3), 5.93
74.1 (C‐5), 83.1 (C‐3), 90.4 (C‐15), 114.4 (C‐17), 132.8 (C‐13),
144.9 (C‐6), 145.6 (C‐12), 153.2 (C‐1′), 194.4 (C‐14); ESI‐MS m/z
2
+
407 [M + H] .
13
(
1H, d, J = 10.4 Hz, H‐5), 7.76 (1H, s, H‐12); C‐NMR (100.61 MHz,
DMSO): δ 8.7 (C‐3″), 9.0 (C‐3′), 12.4 (C‐20), 14.2 (C‐16), 16.3 (C‐19),
2
1
5
1
4
1.4 (C‐8), 25.1 (C‐10), 26.9 (C‐2″), 27.0 (C‐2′), 28.1 (C‐11), 28.6 (C‐
8), 34.8 (C‐9), 35.5 (C‐7), 37.0 (C‐2), 49.1 (C‐1), 52.5 (C‐4), 66.7 (C‐
), 79.7 (C‐3), 87.4 (C‐15), 114.8 (C‐17), 133.2 (C‐13), 145.0 (C‐6),
52.5 (C‐12), 173.0 (C‐1″), 173.6 (C‐1′), 203.9 (C‐14); ESI‐MS m/z
2
.5.7
|
Preparation of euphoboetirane I (11) and 12‐
hydroxyboetirane D (15)
Obtained from reaction of 4 (25 mg, 0.076 mmol) with 73 mg
+
+
69 [M + Na] , 485 [M + K] .
(
0.37 mmol) of 1‐adamantanecarbonyl chloride. The residue was puri-
fied by CC [SiO , 15 g, n‐hexane/EtOAc (1:0 to 0:1)] and preparative
TLC (n‐hexane/EtOAc 4:1, 2×) to give 22 mg of 11 (0.044 mmol,
8% yield) and 5 mg of 15 (0.01 mmol, 13% yield) as amorphous white
2
2
.5.5
|
Preparation of euphoboetirane G (9)
5
Obtained from reaction of 4 (25 mg, 0.075 mmol) with 70 μL
0.55 mmol) of diethylcarbamoyl chloride. The residue was purified
by CC (SiO , 4 g, n‐hexane/EtOAc 1:0 to 0:1, CombiFash system) to
yield 24 mg (0.055 mmol, 73% yield) of an amorphous white solid.
25
1
solids. Euphoboetirane I (11): ½αꢀD + 22 (c 0.100, CHCl
400 MHz, CDCl ): δ 1.13 (3H, d, J = 4.4 Hz, CH ‐16), 1.13 (3H, s,
CH ‐18), 1.18 (3H, s, CH ‐19), 1.40 (1H, dd, d, J = 8.9, 11.1 Hz, H‐
1), 1.65–1.99 (15H, brs, H‐3′ to H‐11′), 2.00 (3H, s, H‐20), 2.13
(1H, m, H‐2), 2.42 (1H, d, J = 8.2 Hz, H‐4), 3.09 (2H, m, H‐1), 4.06
3
); H‐NMR
(
(
3
3
2
3
3
1
2
D
5
1
½
αꢀ + 64 (c 0.090, CHCl
3 3
); H‐NMR (400 MHz, CD OD): δ 1.07
(
3H, d, J = 6.7 Hz, CH
‐18), 1.18 (3H, s, CH
J = 8.5, 11.7 Hz, H‐11), 1.56 (1H, dd, J = 10.5, 13.7 Hz, H‐1β), 1.64
3H, s, CH ‐20), 1.80 (1H, m, H‐8a), 1.91 (1H, m, H‐8b), 2.04 (1H, m,
H‐7b), 2.07 (1H, m, H‐2), 2.34 (1H, m, H‐7a), 2.46 (1H, dd, J = 2.7,
3
‐16), 1.11 (6H, m, H‐3′, H‐3″), 1.17 (3H, s,
(
1H, brs, H‐3), 4.35 (1H, s, H‐17a), 4.87 (1H, s, H‐17b), 5.72 (1H, d,
CH
3
3
‐19), 1.25 (1H, m, H‐9), 1.47 (1H, dd,
1
J = 9.4 Hz, H‐5); H‐NMR (400 MHz, DMSO): δ 0.94 (3H, d,
J = 6.8 Hz, CH
1H, m, H‐9), 1.39 (1H, dd, J = 8.6, 11.8 Hz, H‐11), 1.44 (1H, dd,
J = 11.2, 13.2 Hz, H‐1β), 1.54 (3H, s, CH ‐20), 1.62 (1H, m, H‐8a),
.62 and 1.75 (12H, two brs, H‐3′, H‐5′, H‐7′, H‐8′, H‐10′, H‐11′),
.79 (1H, m, H‐8b), 1.88 (1H, m, H‐7a), 1.89 (1H, m, H‐2), 1.91 (3H,
3 3 3
‐16), 1.08 (3H, s, CH ‐18), 1.12 (3H, s, CH ‐19), 1.13
(
3
(
3
1
0.6 Hz, H‐4), 3.07 (1H, t, J = 11.4 Hz, H‐1α), 3.17 (1H, m, H‐2″),
.29 (1H, m, H‐2′), 4.10 (1H, s, H‐3), 4.67 (1H, s, H‐17a), 4.87 (1H, s,
1
1
3
13
H‐17b), 5.93 (1H, d, J = 10.5 Hz, H‐5), 7.60 (1H, brs, H‐12). C‐
NMR (100.61 MHz, CD OD): δ 12.8 (C‐20), 13.5 (C‐3″), 13.8 (C‐3′),
4.2 (C‐16), 16.7 (C‐19), 22.9 (C‐8), 27.1 (C‐10), 29.2 (C‐18), 30.1
C‐11), 35.9 (C‐7), 37.9 (C‐9), 39.1 (C‐2), 42.2 (C‐2′), 43.2 (C‐2″),
brs, H‐4′, H‐6′, H‐9′), 2.04 (1H, m, H‐7b), 2.28 (1H, dd, J = 1.8,
0.6 Hz, H‐4), 2.92 (1H, t, J = 10.8 Hz, H‐1α), 3.84 (1H, d,
3
1
1
J = 7.2 Hz, 3‐OH), 3.95 (1H, m, H‐3), 4.55 (1H, s, H‐17a), 4.81 (1H,
(
s, H‐17b), 5.48 (1H, s, 15‐OH), 5.99 (1H, d, J = 9.6 Hz, H‐5), 7.53
13
5
1
1
0.5 (C‐1), 55.8 (C‐4), 69.9 (C‐5), 80.6 (C‐3), 90.5 (C‐15), 114.1 (C‐
(
3
1H, brs, H‐12); C‐NMR (100.61 MHz, CDCl ): δ 13.3 (C‐20), 14.6
7), 135.7 (C‐13), 147.3 (C‐6), 154.3 (C‐12), 158.1 (C‐1′), 203.3 (C‐
(
C‐16), 16.2 (C‐19), 19.0 (C‐8), 25.6 (C‐10), 28.0 (C‐4′, C‐6′, C‐9′),
9.9 (C‐18), 34.3 (C‐7), 36.1 (C‐9), 36.5 and 38.9 (C‐3′, C‐5′, C‐7′,
C‐8′, C‐10′, C‐11′), 37.1 (C‐2), 48.7 (C‐1), 55.6 (C‐4), 69.9 (C‐5),
7.8 (C‐3), 113.9 (C‐17), 135.1 (C‐13), 144.5 (C‐6), 178.1 (C‐1′); ESI‐
+
+
4); ESI‐MS m/z 456 [M + Na] , 472 [M + K] .
2
7
2
.5.6
|
Preparation of euphoboetirane H (10)
+
+
MS m/z 519 [M + Na] , 535 [M + K] .
2
5
1
Obtained from reaction of 4 (17 mg, 0.052 mmol) with 70 μL
12‐Hydroxyboetirane D (15): ½αꢀD + 18 (c 0.100, CHCl3); H‐NMR
(
(
0.74 mmol) of ethylchloroformate. The residue was purified by CC
SiO , 4 g, n‐hexane/EtOAc 1:0 to 0:1, CombiFash System) to obtain
(400 MHz, CDCl ): δ 0.50 (1H, d, J = 9.2 Hz, H‐9), 0.59 (1H, m, H‐
3
2
11), 1.04 (3H, d, J = 4.4 Hz, H‐16), 1.04 (3H, s, H‐18), 1.10 (3H, s,
2
D
5
5
mg (0.012 mmol, yield 23%) of a white amorphous solid. ½αꢀ + 27
H‐19), 1.17 (3H, d, J = 8.0 Hz, H‐20), 1.68 and 1.85 (12H, two brs,
H‐3′, H‐5′, H‐7′, H‐8′, H‐10′, H‐11′), 1.80 (1H, m, H‐1α), 1.81 (1H,
m, H‐8b), 1.90 (1H, m, H‐8a), 1.84 (2H, m, H‐7), 2.00 (3H, brs, H‐4′,
H‐6′, H‐9′), 2.10 (1H, t, J = 12.6 Hz, H‐1β), 2.35 (1H, m, H‐2), 2.68
(1H, m, H‐13), 2.86 (1H, dd, J = 2.8, 11.2 Hz, H‐4), 3.46 (1H, s, 3‐
OH), 3.75 (1H, s, H‐3), 4.70 (1H, d, J = 9.2 Hz, H‐12), 4.70 (1H, s, H‐
−
1 1
(
c 0.090, CHCl
3
); IR (KBr) υmax cm
;
H‐NMR (400 MHz, CDCl
): δ 1.12 (3H, s, CH3–19), 1.16 (1H, m, H‐
‐16), 1.24 (3H,
‐3′), 1.25 (1H, m, H‐9), 1.49 (1H, dd, J = 8.3,
1.0 Hz, H‐11), 1.75 (1H, t, J = 13.2 Hz, H‐1β), 1.83 (3H, s, CH
3
): δ
1
H‐NMR (400 MHz, CDCl
3
8
3 3
b), 1.18 (3H, s, CH ‐18), 1.20 (3H, d, J = 6.8 Hz, CH
t, J = 7.2 Hz, CH
3
1
2
2
J
3
‐
13
0), 1.99 (1H, m, H‐8a), 1.97 (1H, m, H‐7b), 2.18 (1H, m, H‐2),
.46 (1H, t, J = 3.9 Hz, H‐4), 2.56 (1H, m, H‐7a), 3.38 (1H, dd,
17a), 4.96 (1H, s, H‐17b), 5.38 (1H, d, J = 11.2 Hz, H‐5); C‐NMR
(100.61 MHz, CDCl ): δ 13.1 (C‐20), 13.5 (C‐16), 15.4 (C‐19), 15.5
3
=
6.7, 13.1 Hz, H‐1α), 4.12 (2H, m, CH
2
‐2′), 4.49 (1H, t,
(C‐10), 23.0 (C‐8), 26.6 (C‐9), 28.0 (C‐4′, C‐6′, C‐9′), 29.2 (C‐18),
30.3 (C‐11), 36.6 and 38.9 (C‐3′, C‐5′, C‐7′, C‐8′, C‐10′, C‐11′), 37.7
(C‐2), 38.2 (C‐7), 41.5 (C‐13), 44.2 (C‐1, C‐2′), 55.2 (C‐4), 69.5 (C‐5),
J = 3.6 Hz, H‐3), 5.46 (1H, d, J = 3.1 Hz, H‐5), 5.08 (1H, s, H‐
13
1
7a), 5.12 (1H, s, H‐17b), 6.39 (1H, d, J = 11.2 Hz, H‐12); C‐
NMR (100.61 MHz, CDCl ): δ 12.5 (C‐16), 12.6 (C‐20), 14.3 (C‐3′),
6.0 (C‐19), 22.6 (C‐8), 26.9 (C‐10), 28.7 (C‐11), 29.2 (C‐18), 33.8
C‐7), 34.5 (C‐9), 37.8 (C‐2), 43.3 (C‐1), 48.3 (C‐4), 64.9 (C‐2′),
74.5 (C‐12),74.9 (C‐3), 87.0 (C‐15), 115.4 (C‐17), 147.3 (C‐6), 179.6
3
+
1
(C‐1′), 220.1 (C‐14); ESI‐MS m/z 519 [M – H
2
O + Na] , 535 [M –
+
(
H
2
O + K] .