Stille–Heck Coupling Sequences
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149.0 (À, Cquat), 167.1 (À, Cquat, C=O); EI-MS (70 eV): m/z (%): 544 (8)
[M +], 488 (20) [M +ÀC4H8], 447 (4), 432 (20) [M +À2C4H8], 431(36)
[M +ÀC4H9ÀC4H8], 385 (12), 356 (29), 311 (86), 299 (78), 255 (74), 237
(32), 195 (15), 143 (19), 91 (4), 75 (43), 57 (100) [C4H9+]; HRMS: m/z:
calcd for C33H56O4Si (544.9): 544.3948 (correct HRMS).
(125 mg, 0.265 mmol) in decalin (2.0 mL) was heated at 2108C for 45 min
to give, after purification by CC on silica gel (14 g, pentane/diethyl ether
5:1), cis-13b as a colorless wax (104 mg, 83%). Rf =0.42; [a]2D0 =+50 (c=
1.00, C6H6); IR (film): n˜ =2975, 2930, 2870, 1721, 1456, 1391, 1366, 1253,
1
1196, 1148, 1061, 948 cmÀ1; H NMR (250 MHz, C6D6): d=1.18 [s, 9H, C-
ACHRTEGNU(CH3)3], 1.22 (s, 3H, CH3), 1.29–1.33 (m, 2H), 1.38 [s, 9H, CO2CACHTREUNG(CH3)3],
tert-Butyl (E)-(1’’S,3a’’S,7a’’S)-3-[8’-(1’’-tert-butoxy-7a’’-methyl-2’’,3’’,3a’’,
6’’,7’’,7a’’-hexahydro-1’’H-indene-5’’-yl)-1’,4’-dioxaspiroACHTREU[NG 4.5]dec-7’-ene-7’-
3
1.25–1.83 (m, 4H), 1.89 (t, J=7.8 Hz, 2H, 1-H), 1.93–2.30 (m, 5H), 2.32–
3
2.63 (m, 3H), 2.65–2.88 (m, 2H), 3.48 (t, J=6.0 Hz, 1H, 17-H), 3.54–3.68
yl]acrylate (trans-12b): According to GP 7, the bromodiene trans-11b
(650 mg, 1.53 mmol) in DMF/CH3CN/H2O 5:5:1(4.4 mL), the palladacy-
cle 14 (57.3 mg, 61.1 mmol), tri-o-tolylphosphane (37.2 mg, 122 mmol),
nBu4NOAc (1.15 g, 3.83 mmol) and tert-butyl acrylate (2.00 mL, 1.75 g,
13.7 mmol) after 4 h at 1058C and work-up with diethyl ether (80 mL),
water (235 mL), back-extraction with diethyl ether (245 mL), brine
(25 mL) and CC on silica gel (50 g, pentane/diethyl ether 5:1) gave trans-
12b as a colorless wax (651mg, 90%). Rf =0.23; IR (film): n˜ =2977,
2931, 2874, 1706, 1615, 1477, 1447, 1390, 1365, 1316, 1291, 1256, 1238,
(m, 4H, C-4’, C-5’); 13C NMR (62.9 MHz, C6D6, DEPT, HMBC, HSQC,
NOESY, H,H-COSY): d=20.1( +, CH3), 22.9 (À, CH2), 24.4 (À, CH2),
28.0 [+, 3C, C
A
(CH3)3], 30.8 (À, CH2), 30.9
(À, CH2), 32.0 (À, CH2), 32.1( À, CH2), 33.9 (À, CH2), 41.2 (À, CH2),
42.8 (Cquat,C-13), 43.7 (+, CH, C-7), 47.6 (+, CH, C-14), 64.3 (À, CH2, C-
4’), 64.3 (À, CH2, C-5’), 72.5 [Cquat, C
80.1( +, CH, C-7), 108.2 (Cquat, C-3), 125.3 (Cquat), 127.5 (Cquat, 2C), 130.5
(Cquat), 172.7 (Cquat, C=O); EI-MS (70 eV): m/z (%): 472 (22) [M +], 416
(46) [M +ÀC4H8], 371 (15), 359 (100) [M +ÀC4H8ÀC4H9], 297 (8), 253
(12), 169 (6), 157 (10), 99 (8), 57 (99) [C4H9+], 41(30); elemental analysis
calcd (%) for C29H44O5 (472.7): C 73.69, H 9.32; found C 73.97, H 8.97.
1197, 1148, 1059, 989, 945, 864, 733 cmÀ1
d=0.83 (s, 3H, CH3), 0.86–1.04 (m, 1H), 1.15 [s, 9H, C
(m, 2H), 1.48 [s, 9H, CO2C
;
1H NMR (250 MHz, CDCl3):
(CH3)3], 1.20–1.44
AHCTREUNG
(CH3)3], 1.48–1.71 (m, 2H), 1.78 (t, 3J=
AHCTREUNG
8.2 Hz, 2H, 9’-H), 1.83–2.25 (m, 4H), 2.36–2.52 (m, 4H), 3.49 (dd, 3J=
9.0, 3J=8.6 Hz, 1H, 1’’-H), 3.91–4.09 (m, 4H, 2’-H, 3’-H), 5.39 (d, 3J=
0.52 Hz, 1H, 4’’-H), 5.65 (d, 3J=16.4 Hz, 1H, 2-H), 7.63 (d, 3J=16.4 Hz,
1H, 3-H); 13C NMR (62.9 MHz, CDCl3, DEPT): d=11.3 (+, CH3), 24.4
tert-Butyl
(+)-(7R,13S,14R,17S)-17-tert-Butoxy-3-methoxy-13-methyl-
2,3,4,6,7,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenan-
threne-7-carboxylate (cis-13c): According to GP 9, cis-12c (120 mg,
0.270 mmol) in decalin (2.00 mL) at 2108C for 45 min, after purification
by CC on silica gel (18 g, pentane/diethyl ether 5:1) gave cis-13c as a col-
orless wax (94.1mg, 78%) with a diastereomeric ratio of 1:1 for the C-3
epimers. Rf =0.50; [a]2D0 =+55 (c=0.100, C6H6); IR (film): n˜ =2979, 2930,
(À, CH2), 26.9 (À, CH2), 28.2 [+, 3C, C
(CH3)3], 29.7 (À, CH2), 31.0 (À, CH2), 31.6 (À, CH2), 33.9 (À, CH2), 35.7
(À, CH2), 41.7 (Cquat, C-7a’’), 43.7 (+, CH, C-3a’’), 64.5 (À, CH2, 2C, C-2’,
C-3’), 72.3 [Cquat, C(CH3)3], 79.2 (+, CH, C-1’’), 79.8 [Cquat, CO2C(CH3)3],
ACHTRE(UNG CH3)3], 28.7 [+, 3C, CO2C-
ACHTREUNG
2869, 1730, 1459, 1390, 1366, 1253, 1197, 1143, 1100 cmÀ1
(250 MHz, C6D6 (distinguishable signals of diastereomers are marked
with #): d=1.18 [s, 9H, C(CH3)3], 1.22 (s, 3H, CH3), 1.26 (s, 3H, CH3)#,
;
1H NMR
A
ACHTREUNG
107.8 (Cquat, C-5’), 117.0 (+, CH, C-2), 125.7 (Cquat), 128.4 (+, CH, C-7’’),
137.3 (Cquat), 143.2 (+, CH, C-3), 148.2 (Cquat), 167.1 (Cquat, C=O); EI-MS
(70 eV): m/z (%): 472 (11) [M +], 416 (50) [M +ÀC4H8], 371(19), 359
(31) [M +ÀC4H9ÀC4H8], 327 (9), 313 (18), 253 (10), 235 (8), 209 (5), 169
(6), 159 (7), 129 (5), 99 (24), 86 (18), 57 (100) [C4H9+], 41(28); elemental
analysis calcd (%) for C29H44O5 (472.7): C 73.69, H 9.32; found C 73.91,
H 9.10.
AHCTREUNG
1.29–1.43 (m, 2H), 1.45 [s, 9H, CO2CCATHRE(UNG CH3)3], 1.46–2.60 (m, 14H), 2.63–
2.94 (m, 2H), 3.21(s, 3H, OCH ), 3.26 (s, 3H, OCH3)#, 3.31–3.48 (m, 1H,
3
H-3), 3.50 (t, J=5.6 Hz, 1H, 17-H); 13C NMR (62.9 MHz, C6D6, DEPT):
3
d=20.0 (+, CH3), 20.2 (+, CH3)#, 22.3 (À, CH2), 22.9 (À, CH2), 24.6 (À,
CH2)#, 27.5 (À, CH2), 28.1[ +, 3C, C
ACHRTUE(NG CH3)3], 28.7 [+, 3C, CO2CACHTREUNG(CH3)3],
28.9 (À, CH2)#, 30.8 (À, CH2, 2C), 30.9 (À, CH2)#, 32.3 (À, CH2), 32.4 (À,
CH2)#, 33.8 (À, CH2), 33.9 (À, CH2)#, 36.4 (À, CH2), 36.6 (À, CH2)#, 42.8
(Cquat, C-13), 43.7 (+, C-7), 43.8 (+, C-7)#, 47.5 (+, C-14), 47.7 (+,C-14)#,
tert-Butyl (E)-(1’’S,3a’’S,7a’’S)-3-[2’-(1’’-tert-Butoxy-7a’’-methyl-2’’,3’’,3a’’,
6’’,7’’,7a’’-hexahydro-1’’H-indene-5’’-yl)-5’-methoxycyclohex-1’-enyl]acry-
late (trans-12c): According to GP 7, the bromobutadiene trans-11c
(250 mg, 0.629 mmol) in DMF/CH3CN/H2O 5:5:1(2.0 mL), the pallada-
cycle 14 (44.0 mg, 50.0 mmol), nBu4NOAc (379 mg, 1.26 mmol) and tert-
butyl acrylate (323 mg, 2.52 mmol) after 4 h at 1058C and work-up with
diethyl ether (70 mL), water (225 mL), back-extraction with diethyl
ether (235 mL), brine (15 mL) and CC on silica gel (52 g, pentane/di-
ethyl ether 5:1) gave trans-12c as a colorless wax (221mg, 79%) with a
diastereomeric ratio of 1:1 for the C-5’ epimers. Rf =0.36; IR (film): n˜ =
2975, 2929, 2822, 1703, 1615, 1458, 1390, 1364, 1313, 1288, 1254, 1194,
1148, 1103, 1071, 984, 897, 853, 732 cmÀ1; 1H NMR (250 MHz, CDCl3, dis-
tinguishable signals of diastereomers are marked with #): d=0.75–0.92
55.4 (+, OCH3), 55.4 (+, OCH3)#, 72.5 [Cquat, C
ACHTREUNG
A
ACHTREUNG
AHCTREUNG
(Cquat), 125.3 (Cquat)#, 127.7 (Cquat, 2C), 127.9 (Cquat, 2C)#, 130.2 (Cquat),
130.5 (Cquat)#, 172.7 (Cquat, C=O), 172.9 (Cquat, C=O)#; EI-MS (70 eV): m/z
(%): 444 (29) [M +], 388 (46) [M +ÀC4H8], 331(82) [ M +ÀC4H8ÀC4H9],
299 (60), 281 (16), 255 (38), 197 (15), 181 (6), 143 (26), 129 (6), 57 (100)
[C4H9+], 41(24); elemental analysis calcd (%) for C 28H44O4 (444.7): C
75.63, H 9.97; found C 75.70, H 10.06.
tert-Butyl (7R,13S,14R,17S)-17-tert-Butoxy-3-(tert-butyldimethylsilanyl-
AHCTREoUGN xy)-13-methyl-2,3,4,6,7,11,12,13,14,15,16,17-dodecahydro-1H-cyclopen-
(m, 1H), 0.98 (s, 3H, CH3), 1.12 [s, 9H, C
1.45 [s, 9H, CO2C
ACHTREUNG
ta[a]phenanthrene-7-carboxylate (cis-13d): According to GP 9, cis-12d
(500 mg, 0.918 mmol) in decalin (15.0 mL) at 2108C for 45 min, after pu-
rification by CC on silica gel (30 g, pentane/diethyl ether 20:1) gave cis-
13d as a colorless wax (452 mg, 90%) with a diastereomeric ratio of 1:1
for the C-3 epimers. Rf =0.41; IR (film): n˜ =2972, 2956, 2930, 2858, 1721,
1472, 1463, 1389, 1367, 1281, 1255, 1196, 1150, 1087, 1062, 1005, 949, 933,
ACHTREUNG
3.31(m, 2H, 5 ’-H, 1’’-H), 5.38 (d, 3J=0.4 Hz, 1H, 4’’-H), 5.97 (d, 3J=
14.9 Hz, 1H, 2-H), 7.60 (d, 3J=14.9 Hz, 1H, 3-H); 13C NMR (62.9 MHz,
CDCl3, DEPT): d=11.6 (+, CH3), 24.8 (À, CH2), 27.2 (À, CH2), 27.3 (À,
CH2)#, 27.5 (À, CH2), 27.6 (À, CH2)#, 28.3 [+, 3C, C
(CH3)3], 28.7 (À,
U
CH2), 28.8 (À, CH2)#, 28.9 [+, 3C, CO2C
(CH3)3], 31.3 (À, CH2), 32.0 (À,
U
909, 870, 836, 814, 775, 733, 670, 647 cmÀ1
(distinguishable signals of diastereomers are marked with #): d=0.04 [s,
6H, Si(CH3)2], 0.92 [s, 9H, SiC(CH3)3], 0.95 (s, 3H, CH3), 1.18 [s, 9H, C-
(CH3)3], 1.41–2.36 (m,
;
1H NMR (250 MHz, CDCl3,
CH2), 34.1( À, CH2), 34.2 (À, CH2)#, 42.1(C quat, C-7a’’), 43.7 (+, CH, C-
3a’’), 55.5 (+, OCH3), 72.1[C quat, CCATHRE(UNG CH3)3], 75.0 (+, CH, C-1’’), 75.3 (+,
A
ACHTREUNG
CH, C-1’’)#, 79.2 (+, CH, C-5’), 79.3 (+, C-5’)#, 79.4 [Cquat, CO2C
ACHTRE(UNG CH3)3],
ACHRTE(UGN CH3)3], 1.20–1.32 (m, 5H), 1.38 [s, 9H, CO2CACHTREUNG
117.4 (+, CH, C-2), 125.9 (Cquat), 126.0 (Cquat)#, 128.2 (+, CH, C-4’’),
128.2 (+, CH, C-4’’)#, 138.1 (Cquat), 138.1 (Cquat)#, 143.9 (+, CH, C-3),
148.9 (Cquat), 148.9 (Cquat)#, 166.9 (Cquat, C=O); EI-MS (70 eV): m/z (%):
444 (4) [M +], 388 (46) [M +ÀC4H8], 356 (41), 331 (31) [M +
ÀC4H9ÀC4H8], 311(92), 299 (38), 281(30), 255 (36), 253 (46), 237 (29),
197 (18), 169 (51), 140 (43), 129 (16), 91 (11), 81 (6), 57 (100) [C4H9+], 41
(27); elemental analysis calcd (%) for C28H44O4 (444.7): C 75.63, H 9.97;
found C 75.42, H 9.86.
12H), 2.69–2.80 (m, 2H), 3.52 (t, 3J=5.3 Hz, 1H, 17-H), 3.78 (m, 1H, 3-
H), 3.88 (m, 1H, 3-H)#; 13C NMR (75.6 MHz, C6D6, APT): d=À4.6 [+,
2C, Si
N
CH2), 22.8 (À, CH2)#, 24.8 (À, CH2), 25.9 [+, 3C, SiC
ACHTRE(UGN CH3)3], 28.0 [+,
3C, C
A
31.7 (À, CH2), 31.9 (À, CH2)#, 32.6 (À, CH2), 33.5 (À, CH2), 33.8 (À,
CH2)#, 40.2 (À, CH2), 40.4 (À, CH2)#, 42.1( À, Cquat,C-13), 43.2 (+, CH,
C-7), 43.7 (+, CH, C-7)#, 47.2 (+, CH, C-14), 47.6 (+, CH, C-14)#, 67.6
(+,CH, C-3)#, 68.6 (+,CH, C-3)#, 72.6 [À, Cquat, C
tert-Butyl (+)-(7R,13S,14R,17S)-17-tert-butoxy-13-methyl-spiro(1’,3’-di-
A
N
C
A
(+, CH, C-17), 80.0 (+, CH, C-17)#, 124.3 (À, Cquat)#, 125.1 (À, Cquat),
Chem. Eur. J. 2007, 13, 3739 – 3756
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3751