U. Muellner et al. / Tetrahedron 56 (2000) 3893±3899
3897
CDCl3): d 16.28 (q, C-19), 16.46 (q, C-20), 17.13 (q,
C-16p), 17.77 (q, C-17p), 18.44 (t, C-2), 21.32 (t, C-11),
23.57 (t, C-12), 28.55 (t, C-6), 34.35 (d, C-15), 35.04 (t,
C-1), 36.46 (t, C-3), 36.73 (s, C-10), 40.37 (d, C-5), 47.17
(s, C-4), 52.14 (q, C-21), 54.29 (d, C-14), 59.57 (s, C-13),
60.99 (s, C-8), 68.51 (d, C-7), 71.11 (s, C-9), 179.5 (s, C-21)
ppm; C21H32O5, MS (70 eV, EI): m/z (%): 346 (2)
[M12H2O], 335 (2), 318 (5), 303 (6), 278 (5), 275 (13),
258 (5), 243 (8), 199 (100), 123 (20), 109 (10).
Methyl-1S-[2a, 3aa,4a,7aa]-spiro-[30-oxo-60-(1-methyl-
10,60
ethyl)-70-oxabicyclo[4.1.0.] heptane-1,20-[1H]-2,3,3a,4,
5,6,7,7a-octahydro-2-hydroxy-4,7a-dimethyl-indene-4-
carboxylate] (11). White crystals, mp 151±1528C; Rf0.64
(cyclohexane/AcOEt1:1); UV (CH2Cl2): l (log e)
230.6 nm (2.60), 223.4 nm (2.22); [a]2D12135.0, (c0.16
CH2Cl2), IR (KBr) vÄ: 3490, 2942, 2877, 1724, 1688, 1462,
1
1247, 1204, 1198, 1034 cm21; H NMR (400 MHz, C6D6):
d 0.92 (d, 3H, 90-Hp, J6.9 Hz), 0.94 (m, 1H, 5-Hax), 0.96
(m,1H, 7-Hax), 0.98 (d, 3H, 100-H, J6.9 Hz), 1.02 (s, 3H,
8-H), 1.13 (s, 3H, 10-H), 1.37 (dquint, 1H, 6-Heq,
J13.7 Hz, J3.5 Hz), 1.53 (sept, 1H, 80-H, J6.9 Hz),
1.60 (dm, 1H, 7-Heq, J13.2 Hz), 1.72 (ddd, 1H, 3-Heq,
J14.6 Hz, J11.8 Hz, J10.4 Hz), 1.75 (m, 2H, 50-Hax,
50-Heq), 1.90 (qt, 1H, 6-Hax, J13.7 Hz, J3.4 Hz), 2.00 (d,
1H, 2-OH, J10.8 Hz), 2.02 (m, 1H, 40-Heq), 2.06 (ddd, 1H,
3-Hax, J14.6 Hz, J10.4 Hz, J4.5 Hz), 2.10 (dt, 1H,
5-Heq), 2.50 (td, 1H, 40-Hax, J7.1 Hz, J13.7 Hz), 2.85
(s, 1H, 10-H), 3.4 (t, 1H, 3a-H, J10.4 Hz), 4.00 (ddd,
1H, 2-H, J11.8 Hz, J10.8 Hz, J4.5 Hz) ppm; 13C
(100 MHz, C6D6): d 17.82 (q, C-90), 18.23 (q, C-100),
19.38 (t, C-6), 20.75 (q, C-10), 21.95 (t, C-50), 26. 84 (q,
C-8), 29.33 (t, C-5), 29.85 (t, C-7), 34.12 (d, C-80), 37.09 (t,
C-3), 38.63 (t, C-40), 42.99 (s, C-4), 46.52 (d, C-3a), 49.76
(s, C-7a), 51.12 (q, OCH3), 61.74 (s, C-60), 62.43 (d, C-10),
65.66 (s, C-1), 77.01 (d, C-2), 177.65 (s, C-9), 212.9 (s,
C-30) ppm; MS (EI, 70 eV): m/z (%); 346 (8) [M12H2O],
321 (18), 303 (30), 261 (4), 243 (20), 215 (7), 182 (47), 123
(100); Anal. Calcd for C21H32O5: C, 69.2; H, 8.85; found: C,
69.17; H, 8.85.
Methyl-1R-[2a,3aa,4a,7aa]-spiro-[30-oxo-60-(1-methyl-
10,60
ethyl)-70-oxabicyclo[4.1.0] heptan-1,20-[1H]-2,3,3a,4,5,
6,7,7a-octahydro-2-hydroxy-4,7a-dimethyl-4-indene-car-
boxylate] (9). White crystals, mp 181±1828C; Rf0.50 (cy-
clohexane/AcOEt 1:1); UV (CH2Cl2):
l
(log e)
229.6 nm (1.795), 224 nm (1.475); [a]2D2267.6 (c0.37,
CH2Cl2); IR (KBr) vÄ: 3522, 2959, 2929, 2870, 1727, 1701,
1463, 1262, 1103 cm21; 1H NMR (600 MHz, C6D6): d 0.62
(dt, 1H, 7-Heq), 0.86 (d, 3H, 90-Hp, J6.9 Hz), 0.93 (d, 3H,
100-Hp, J6.9 Hz), 0.95 (td, 1H, 5-Hax, J13.6 Hz, J
4.0 Hz), 0.96 (s, 3H, 8-H), 0.99 (s, 3H, 10-H), 1.32 (dquint,
1H, 6-Heq, J14.4 Hz, J3.2 Hz), 1.38 (td, 1H, 7-Hax,
J13.6 Hz, J4.3 Hz), 1.45 (sept, 1H, 80-H, J6.9 Hz),
1.70 (qt, 1H, 6-Hax, J13.8 Hz, J3.6 Hz), 1.75 (m, 2H,
50-Hax, 50-Heq), 1.90 (m, 2H, 40-Heq, 3-H), 2.00 (m, 1H,
3-H), 2.00 (dt, 1H, 5-Heq), 2.30 (ddd, 1H, 40-Hax, J
16.4 Hz, J9.1 Hz, J7.3 Hz), 3.05 (dd, 1H, 3a-H, J
11.8 Hz, J9.3 Hz), 3.51 (s, 1H, 10-H), 5.36 (dd, 1H, 2-H,
J9.2 Hz, J3.2 Hz) ppm; 13C (100 MHz, C6D6): d 17.84
(q, C-16), 17.98 (q, C-9p), 19.53 (t, C-6), 20.92 (q, C-10),
21.26 (t, C-50), 27.15 (q, C-8), 28.96 (t, C-5), 30.59 (t, C-7),
33.72 (t, C-3), 34.59 (d, C-80), 35.46 (t, C-40), 43.19 (s, C-4),
47.56 (s, C-7a), 51.17 (q, OCH3), 62.50 (s, C-60), 62.77 (d,
C-10), 67.56 (s, C-1(20)), 73.49 (d, C-2), 177.73 (s, C-9),
208.32 (s, C-30) ppm; MS (70 eV, EI): m/z (%): 364 (10)
[M1], 346 (74), 331 (40), 314 (17), 286 (24), 268 (29), 251
(100), 243 (40), 207 (29), 153 (30), 123 (20), 107 (33); Anal.
Calcd for C21H32O5: C, 69.2; H, 8.85; found: C, 69.0; H, 8.79.
Methyl-[1R-(1a,4ab,4ba,7a,8aa,9a,10aa)]-4b,8a-epoxy-
tetradecahydro-1,4a-dimethyl-7,8,9-trihydroxy-7-(1-methyl-
ethyl)-1-phenanthrene-carboxylate (15). Colourless resin;
Rf0.65 (cyclohexane/AcOEt1:1); UV: ±; IR (KBr) vÄ:
1
3481, 2931, 1724, 1459, 1389, 1255, 1072, 729 cm21; H
NMR (400 MHz, C6D6): d 0.98 (s, 3H, 18-H), 0.98 (d, 3H,
16-Hp, J6.9 Hz), 1.10 (s, 3H, 19-H), 1.12 (dt, 1H, 6-Heq),
1.20 (1H, m, 12-Hax), 1.24 (d, 3H, 17-Hp, J6.9 Hz), 1.20±
1.40 (m, 2H, 1-H), 1.28±1.50 (m, 2H, 2-H), 1.50±1.60 (m,
2H, 3-H), 1.54 (dt, 1H, 11-Heq), 1.56 (1H, m, 12-Heq), 1.74
(ddd, 1H, 6-Hax, J14.0 Hz, J12.2 Hz, J3.2 Hz), 2.14
(sept, 1H, 15-H, J6.9 Hz), 2.18 (td, 1H, 11-Hax), 2.28 (d,
1H, 5-H, J12.1 Hz), 2.35 (d, 1H, 14-OH, J10.8 Hz), 2.45
(d, 1H, 7-OH, J7.0 Hz), 3.50 (s, 3H, 21-H), 4.35 (ddd, 1H,
7-H), 4.90 (dd, 1H, 14-H, J10.8 Hz, J1.7 Hz) ppm; 13C
(100 MHz, C6D6): d 16.39 (q, C-18), 16.84 (q, C-19), 17.24
(q, C-16p), 17.42 (q, C-17p), 18.86 (t, C-2), 22.40 (t, C-11),
24.57 (t, C-12), 28.47 (t, C-6), 33.87 (d, C-15), 35.98 (t,
C-1), 36.40 (t, C-3), 37.69 (s, C-10), 40.58 (d, C-5), 47.36
(s, C-4), 51.69 (q, C-21), 67.23 (d, C-7), 67.69 (d, C-14),
67.85 (s, C-8), 76.72 (s, C-9), 78.48 (s, C-13), 178.22 (s,
C-20) ppm; C21H34O6, MS (70 eV, EI): m/z (%): 382 (8)
[M1], 364 (10), 347 (49), 329 (20), 307 (23), 269 (30),
243 (38), 214(33), 189 (28), 183 (39), 175 (87), 147 (41),
123 (100).
Methyl-[1R-(1a,4ab,4ba,7a,8aa,9a,10aa)]-4b,8a-epoxy-
tetradecahydro-1,4a-dimethyl-9-hydroxy-7-(1-methylethyl)-
8-oxo-1-phenanthrene-carboxylate (10). Colourless resin;
Rf0.77 (cyclohexane/AcOEt1:1); UV: ±; [a]2D2237.26
(c0.21, CH2Cl2); IR (KBr) vÄ: 3439, 2955, 1873, 1726,
1462, 1386, 1252, 1071 cm21
;
1H NMR (400 MHz,
CDCl3): d 0.78 (d, 3H, 16-Hp), 0.88 (d, 3H, 17-Hp,
J6.9 Hz), 1.07 (s, 3H, 19-H), 1.12 (s, 3H, 20-H), 1.06
(dt, 1H, 6-Heq), 1,50±1,70 (m, 2H, 2-Hax, 2-Heq), 1.52 (m,
2H, 1-H, 3-H), 1.70 (m, 1H, 1-H), 1.60 (dt, 1H, 6-Hax,
J4.1 Hz, J10.9 Hz, J13.9 Hz), 1.82 (m, 1H, 3-H),
1.60 (m, 1H, 11-Hax), 1.80 (m, 1H, 11-Heq), 1.80 (m, 1H,
12-Heq), 1.85 (m, 1H, 13-H), 2.20 (m, 1H, 12-Hax), 2.22 (d,
1H, 5-H, J12 Hz), 2.40 (m, 1H, 15-H), 3.20 (s, br, 1H,
OH), 3.65 (s, 3H, 21-H), 4.50 (m, 1H, 7-H) ppm; 13C
(100 MHz, CDCl3): d 15.80 (t, C-2), 16.58 (2C, q,
C-19,20), 17.79 (q, C-16p), 18.60 (t, C-11), 19.90 (q,
C-17p), 23.75 (t, C-12), 26.75 (t, C-6), 28.08 (d, C-15),
34.82 (t, C-1), 35.66 (t, C-3), 37.60 (s, C-10), 40.19 (d,
C-5), 47.61 (s, C-4), 51.97 (q, C-21), 53.08 (d, C-13), 65.34
(d, C-7), 65.56 (s, C-9), 74.02 (s, C-8), 179.5 (s, C-18), 210.50
(s, C-14) ppm; C21H32O5, MS (70 eV, EI): m/z (%):364 (16)
[M1], 346 (40), 331 (28), 286 (16), 253 (22), 243 (28), 207
(16), 183 (97), 153 (52), 123 (100), 109 (31).
Isomerisation of 4 with hemin (general procedure)
Under Ar 4 (1 equiv.) was dissolved in a 1:1 mixture of
MeCN/aqueous phosphate buffer (pH 7.8). l-Cysteine
(1 equiv.) was added, followed by hemin (0.1±1 equiv.).
The mixture was stirred at room temperature for 4±65 h,