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12 Yields refer to isolated and chromatographically
pure compounds. All the compounds exhibited spectroscopic data (IR, ¹H
and ¹³C NMR and HRMS) consistent with
their structures. Spectroscopic data for (1R,2S,6R,8S,10R)-10-methoxy-2-methyltricyclo[6.3.0.0²,6]undec-3-en-5-one
(19): [α]D
²¹ -76.8
(c 4.6, CHCl3); IR (neat):
1710, 1589, 1366, 1342, 1265, 1185, 1110, 1004, 836, 817, 784 cm-¹; ¹H
NMR (300 MHz, CDCl3): δ = 7.39 (d, J = 5.4 Hz, 1 H,
H-3), 6.02 (d, J = 5.4 Hz,
1 H, H-4), 3.83 (tt, J = 8.7,
6.3 Hz, 1 H, H-10), 3.28 (s, 3 H, OCH3),
2.36 (dd, J = 9.9, 1.5 Hz,
1 H, H-6), 2.25-1.90 (m, 6 H), 1.59 (dd, J = 11.4, 8.1 Hz, 1 H),
1.46 (dd, J = 13.5, 5.1 Hz,
1 H), 1.29 (s, 3 H, tert-CH3); ¹³C
NMR (100 MHz, CDCl3): δ = 212.8 (C,
C=O), 172.0 (CH, C-3), 131.3 (CH, C-4), 83.7 (CH, C-10),
58.0 (CH, C-6), 57.0 (CH3, OCH3), 55.1 (C,
C-2), 49.5 (CH, C-1), 40.9 (CH, C-8), 37.0 (CH2), 36.1
(CH2), 33.5 (CH2), 21.5 (CH3, tert-CH3); HRMS: m/z calcd
for C13H18O2Na [M + Na]:
229.1205; found: 229.1208.
(1R,2S,6S,8S,10R)-6-Allyl-10-methoxy-2,5-dimethyl-tricyclo[6.3.0.0²,6]undec-4-en-3-one
(23): [α]D
²5 -29.8
(c 3.5, CHCl3); IR (neat):
1701, 1622, 1374, 1285, 1111, 995, 915, 865 cm-¹; ¹H
NMR (300 MHz, CDCl3): δ = 5.91 (s,
1 H, H-4), 5.60 (ddt, J = 16.8,
9.9, 7.2 Hz, 1 H, CH=CH2), 5.06
(dd, J = 16.7, 1.8 Hz,
1 H, CH=CH
2),
5.01 (dd, J = 9.9, 1.8 Hz,
1 H, CH=CH
2),
3.78 (tt, J = 8.4, 5.7 Hz,
1 H, H-10), 3.28 (s, 3 H, OCH3), 2.50-2.37
(m, 2 H), 2.26 (dt, J = 12.0, 7.5 Hz,
1 H), 2.15-1.85 (m, 4 H), 2.02 (s, 3 H,
olefinic CH3), 1.69-1.55 (m, 1 H),
1.49 (dd, J = 15.3, 8.4 Hz,
1 H), 1.41 (dd, J = 15.3,
4.5 Hz, 1 H), 1.09 (s, 3 H, tert-CH3); ¹³C
NMR (100 MHz, CDCl3): δ = 212.9 (C,
C=O), 180.4 (C, C-5), 134.6 (CH, CH=CH2),
130.2 (CH, C-4), 117.6 (CH2, CH=CH2), 83.2 (CH, C-10), 61.6
(C, C-2), 59.0 (C, C-6), 57.0 (CH3, OCH3),
51.1 (CH, C-1), 41.7 (CH2), 39.0 (CH2), 37.8
(CH, C-8), 35.7 (CH2), 33.5 (CH2), 15.6 (CH3),
15.4 (CH3); HRMS: m/z calcd for C17H24O2Na [M + Na]: 283.1674;
found: 283.1662.
Ethyl 4-[(1R,2S,6S,8S,10R)-10-methoxy-2,5-dimethyl-3-oxotricyclo[6.3.0.0²,6]undec-4-en-6-yl]but-2-enoate
(25): [α]D
²0 -60.6
(c 3.3, CHCl3); IR (neat):
1713, 1704, 1652, 1622, 1460, 1442, 1370, 1269, 1219, 1184, 1099,
1039, 977, 867 cm-¹; ¹H
NMR (400 MHz, CDCl3): δ = 6.67 (dt, J = 15.6, 7.9 Hz, 1 H,
H-3), 5.89 (s, 1 H, H-4′), 5.78 (d, J = 15.6 Hz, 1 H,
H-2), 4.09 (q, J = 7.1 Hz,
2 H, OCH
2CH3), 3.80-3.65
(m, 1 H, H-10′), 3.21 (s, 3 H, OCH3),
2.52 (dd,
J = 15.8,
6.5 Hz, 1 H, H-4), 2.45 (dd, J 15.7,
8.2 Hz, 1 H, H-4), 2.27-2.20 (m, 2 H),
2.15-1.75 (m, 3 H), 1.96 (s, 3 H, olefinic-CH3),
1.61 (t, J = 12.4 Hz,
1 H), 1.47-1.34 (m, 2 H), 1.21 (t, J = 7.1 Hz, 3 H,
OCH2CH
3), 1.01
(s, 3 H, tert-CH3); ¹³C
NMR (100 MHz, CDCl3): δ = 212.3 (C,
C=O), 179.2 (C, C-5′), 165.6 (C, OC=O),
144.6 (CH, C-3), 130.7 (CH, C-4′), 123.9 (CH, C-2), 83.1
(CH, C-10′), 61.3 (C, C-2′), 60.2 (CH2,
OCH2CH3), 59.3
(C, C-6′), 57.0 (CH3, OCH3), 51.1 (CH,
C-1′), 41.6 (CH2), 37.9 (CH, C-8′),
37.6 (CH2), 35.6 (CH2), 33.6 (CH2),
15.9 (CH3), 15.5 (CH3), 14.2 (CH3); HRMS: m/z calcd
for C20H28O4Na [M + Na]:
355.1886; found: 355.1894.
2-[(1S,3S,5R,7R,8S,11S,12R)-5-Methoxy-8,11-dimethyl-9-oxotetracyclo[6.6.0.0¹,¹¹.0³,7]tetradecan-12-yl]propan-2-ol (28x, norcrinipellin): m.p. 118-119 ˚C; [α]D
²4 -64.6
(c 1.4, CHCl3); IR (KBr):
3473 (OH), 2959, 2880, 1731 (C=O), 1460, 1373, 1225, 1108,
949 cm-¹; ¹H
NMR (400 MHz, CDCl3): δ = 3.77 (tt, J = 8.4, 6.4 Hz, 1 H,
H-5), 3.29 (s, 3 H, OCH3), 2.75 (d, J = 17.8 Hz, 1 H,
H-10A), 2.37-2.15 (m, 2 H), 2.14 (d, J = 17.8 Hz, 1 H,
H-10B), 2.15-1.90 (m, 4 H), 1.86-1.30
(m, 8 H), 1.32 (s, 3 H, tert-CH3),
1.22 (s, 3 H, tert-CH3),
1.20 (s, 3 H, tert-CH3),
1.12 (s, 3 H, tert-CH3); ¹³C NMR
(100 MHz, CDCl3): δ = 224.4 (C, C=O),
82.9 (CH, C-5), 72.9 (C, C-OH), 65.9 (C, C-1), 60.8 (C, C-8), 57.3
(CH3, OCH3), 57.2 (CH, C-12), 53.6 (CH, C-7),
52.0 (CH2), 49.4 (C, C-11), 43.5 (CH2), 39.5
(CH, C-3), 37.1 (CH2), 34.3 (CH2), 33.0 (CH2),
31.3 (CH3) and 30.2 (CH3) [2 × tert-CH3], 25.0 (CH2),
18.9 (CH3) and 17.8 (CH3) [2 × tert-CH3]; HRMS: m/z calcd
for C20H32O3Na [M + Na]:
343.2250; found: 343.2238; Anal. Calcd. for C20H32O3:
C, 74.96; H, 10.06. Found: C, 74.95; H, 10.17.
2-[(1S,3S,5R,7R,8S,11S,12S)-5-Methoxy-8,11-dimethyl-9-oxotetracyclo[6.6.0.0¹,¹¹.0³,7]tetradecan-12-yl]propan-2-ol (28n, 12-epinorcrinipellin): [α]D
²³ +4.0
(c 1.0, CHCl3); IR (neat):
3469, 1729, 1371, 1257, 1220, 1113, 942 cm-¹; ¹H NMR
(400 MHz, CDCl3): δ = 3.77 (quint., J = 7.3 Hz, 1 H, H-5),
3.28 (s, 3 H, OCH3), 3.19 (d, J = 17.0 Hz,
1 H, H-10A), 2.48 (dt, J = 12.0,
7.6 Hz, 1 H), 2.26 (dd, J = 13.8, 6.8 Hz,
1 H), 2.20-2.04 (m, 2 H), 2.00 (d, J = 17.0 Hz, 1 H, H-10B),
2.05-1.90 (m, 2 H), 1.80-1.65 (m, 2 H),
1.64 (dd,
J = 10.9,
6.3 Hz, 1 H), 1.55-1.35 (m, 5 H),
1.32 (s, 3 H, tert-CH3),
1.24 (s, 3 H, tert-CH3),
1.21 (s, 3 H, tert-CH3),
1.02 (s, 3 H, tert-CH3); ¹³C
NMR (100 MHz, CDCl3): δ = 222.6 (C, C=O),
83.5 (CH, C-5), 72.6 (C, C-OH), 65.4 (C, C-1), 59.1 (CH, C-12),
59.0 (C, C-8), 57.1 (CH3, OCH3), 50.3 (CH,
C-7), 47.1 (C, C-11), 46.8 (CH2), 45.7 (CH2),
40.0 (CH, C-3), 37.3 (CH2), 34.9 (CH2), 33.6
(CH2), 31.7 (CH3), 30.8 (CH3), 27.2
(CH2), 27.1 (CH3), 17.2 (CH3);
HRMS: m/z calcd
for C20H32O3Na [M + Na]:
343.2250; found: 343.2241.
(1S,3S,5R,7R,8S,11S,12S)-12-Isopropenyl-5-methoxy-8,11-dimethyltetracyclo[6.6.0.0¹,¹¹.0³,7]tetradecan-9-one
(31x): [α]D
²² -22.5
(c 0.4, CHCl3); IR (neat):
1733, 1637, 1376, 1257, 1223, 1192, 1117, 891 cm-¹; ¹H
NMR (400 MHz, CDCl3): δ = 4.86 (s,
1 H, C=CH2), 4.68 (s, 1 H,
C=CH2), 3.77 (quint., J = 7.0 Hz,
1 H, H-5), 3.29 (s, 3 H, OCH3), 2.56 (d, J = 17.8 Hz, 1 H,
H-10A), 2.34-2.25 (m, 2 H), 2.17-1.75 (m,
6 H), 1.73 (s, 3 H, olefinic CH3),
1.74-1.60 (m, 3 H), 1.51-1.40 (m, 2 H),
1.31 (dd, J = 11.0, 6.8 Hz,
1 H), 1.10 (s, 3 H, tert-CH3),
0.93 (s, 3 H, tert-CH3); ¹³C
NMR (100 MHz, CDCl3): δ = 223.6 (C,
C=O), 144.3 (C, C=CH2),
113.3 (CH2, C=CH2),
83.0 (CH, C-5), 64.7 (C, C-1), 61.2 (C, C-8), 57.2 (CH3,
OCH3), 56.3 (CH, C-12), 52.9 (CH, C-7), 50.5 (CH2, C-10),
49.5 (C, C-11), 44.6 (CH2), 39.7 (CH, C-3), 37.1 (CH2),
34.1 (CH2), 33.7 (CH2), 27.4 (CH2),
23.4 (CH3), 18.3 (CH3), 18.1 (CH3);
HRMS: m/z calcd
for C20H30O2Na [M + Na]:
325.2145; found: 325.2139.
(1S,3S,5R,7R,8S,11S,12R)-12-Isopropenyl-5-methoxy-8,11-dimethyltetracyclo[6.6.0.0¹,¹¹.0³,7]tetradecan-9-one (31n): [α]D
²4 -60.0
(c 0.6, CHCl3); IR (neat):
1732, 1637, 1377, 1261, 1223, 1191, 1115, 1019, 891, 801 cm-¹; ¹H NMR
(400 MHz, CDCl3): δ = 4.86 (s, 1 H,
C=CH2), 4.69 (s, 1 H, C=CH2],
3.77 (quint., J = 7.3 Hz,
1 H, H-5), 3.28 (s, 3 H, OCH3), 2.55-2.40
(m, 1 H), 2.45 (d, J = 17.1 Hz,
1 H, H-10A), 2.17-2.00 (m, 4 H), 2.00-1.88
(m, 2 H), 1.87 (d,
J = 17.1 Hz,
1 H, H-10B), 1.74 (s, 3 H, olefinic CH3),
1.66-1.60 (m, 1 H), 1.53-1.40 (m, 4 H),
1.31 (dd, J = 11.0, 6.8 Hz, 1 H),
1.18 (s, 3 H, tert-CH3),
1.02 (s, 3 H, tert-CH3]; ¹³C NMR
(100 MHz, CDCl3): δ = 221.7 (C, C=O),
144.8 (C, C=CH2),
112.9 (CH2, C=CH2),
83.6 (CH, C-5), 64.2 (C, C-1), 59.6 (C, C-8), 57.3 (CH3,
OCH3), 57.1 (CH, C-12), 50.6 (CH, C-7), 47.3 (C, C-11),
46.4 (CH2, C-10), 45.7 (CH2), 40.1 (CH, C-3),
37.2 (CH2), 34.8 (CH2), 33.5 (CH2),
29.5 (CH2), 25.1 (CH3), 23.9 (CH3),
16.9 (CH3); HRMS: m/z calcd for C20H30O2Na [M + Na]:
325.2145; found: 325.2140.
Crystal data for norcrinipellin
(28x): X-ray data were collected at 296
K with a SMART CCDBRUKER diffractometer with graphite-monochromated
MoKα radiation (0.71073 Å). The structure
was solved by direct methods (SIR 92). Refinement was by full-matrix
least-squares procedures on F2 using SHELXL-97. The nonhydrogen
atoms were refined anisotropically, whereas hydrogen atoms were
refined isotropically. Molecular formula C20H32O3;
MW = 320.5; T = 296
(2) K; Crystal system: monoclinic; Space group: P21;
cell parameters: a = 9.5828
(4) Å; b = 8.1659
(4) Å; c = 11.7728
(5) Å; α = 90
(0)˚; β = 101.3
(3)˚; γ = 90
(0)˚; V = 903.6
(7) ų; Z = 2; D
calcd = 1.18
g˙cm-³; F(000) = 352; µ = 0.077
mm-¹; Total number of l.s. parameters = 212; R: = 0.068
for 1789
[I > 2σ(I)]; wR2 = 0.216
and 0.0961 for all 12211 data; GOF = 1.019;
Restrained GOF = 1.019 for all data;
An ORTEP diagram is depicted in Figure
[²]
. Crystallographic data
have been deposited with the Cambridge Crystallographic Data Centre
(CCDC 831696).
