M. Schelper, A. de Meijere
FULL PAPER
853, 803, 738, 703 cmϪ1
.
1H NMR (250 MHz, CDCl3): δ ϭ 0.29 (Cquat, C-8Ј), 118.77 (Ϫ, CϭCH2), 128.29 (Cquat, C-6Ј*), 129.74
(mc, 2 H, Cpr-H), 0.57 (mc, 2 H, Cpr-H), 1.18 [s, 9 H, C(CH3)3], (Cquat, C-3Ј*), 132.15 (Cquat, C-2Ј), 134.18 (Cquat, C-1Ј), 136.37 (ϩ,
1.83 (br. s, 2 H, 5Ј-H), 3.02 (br. s, 2 H, 7Ј-H), 3.27 (mc, 2 H, 9Ј-H), CϭCH2), 172.76 (Cquat, 2 C, CϭO) ppm. MS (EI, 70 eV): m/z
3.74 (s, 6 H, OCH3), 4.64 (dd, 3J ϭ 17.7, 2J ϭ 2.6 Hz, 1 H, Cϭ
(%) ϭ 402 (12) [Mϩ], 359 (100) [Mϩ Ϫ C2H4 Ϫ CH3], 345 (47)
3
2
CH2), 4.94 (dd, J ϭ 11.0, J ϭ 2.6 Hz, 1 H, CϭCH2), 6.22 (dd,
[Mϩ Ϫ C4H9], 317 (30) [Mϩ Ϫ C4H9 Ϫ C2H4], 285 (27) [Mϩ
Ϫ
3J ϭ 17.7, 3J ϭ 11.0 Hz, 1 H, HCϭCH2) ppm. 13C NMR TBDMS Ϫ H2], 227 (18), 167 (31), 89 (61), 73 (62). C23H34O4Si
(62.9 MHz, CDCl3, DEPT): δ ϭ 10.14 (Ϫ, 2 C, Cpr-C), 19.71
(Cquat, Cpr-C), 32.38 [ϩ, 3 C, C(CH3)3], 34.29 (Ϫ, C-5Ј), 36.26
[Cquat, C(CH3)3], 42.57 (Ϫ, C-9Ј), 44.15 (Ϫ, C-7Ј), 52.76 (ϩ, 2 C,
OCH3), 58.99 (Cquat, C-8Ј), 116.37 (Ϫ, CϭCH2), 131.21 (Cquat, C-
6Ј*), 133.05 (Cquat, C-3Ј*), 136.45 (Cquat, C-2Ј), 136.67 (ϩ, Cϭ
CH2), 139.57 (Cquat, C-1Ј), 172.68 (Cquat, 2 C, CϭO) ppm. MS
(200 eV, DCI, NH3): m/z (%) ϭ 706 (3) [2 M ϩ NH4ϩ], 362 (100)
[M ϩ NH4ϩ], 345 (48) [M ϩ Hϩ]. C21H28O4 (344.4): calcd. C 73.23,
H 8.19; found C 73.08, H 7.98.
(402.6): calcd. C 68.62, H 8.51; found C 68.84, H 8.32.
Dimethyl Spiro{cyclopropane-1,4Ј-[2Ј-(6ЈЈ-heptenyl)-3Ј-vinylbicyclo-
[4.3.0]nona-1Ј(6Ј),2Ј-diene-8Ј,8Ј-dicarboxylate]} (21-Hept): Accord-
ing to GP2, Pd(OAc)2 (22.4 mg, 100 µmol, 10 mol %), PPh3
(78.6 mg, 300 µmol, 30 mol %), K2CO3 (276 mg, 2.00 mmol) and
dimethyl 2-bromotetradeca-1,13-dien-6-yne-4,4-dicarboxylate (5-
Hept, 385 mg, 999 µmol) were stirred in DMF (10 mL) with bi-
cyclopropylidene (160 mg, 2.00 mmol) at 110 °C for 12 h. Column
chromatography on silica gel (120 g, 4 ϫ 25 cm, pentane/diethyl
ether, 10:1, Rf ϭ 0.45) yielded 21-Hept (185 mg, 48%) as a pale
yellow oil. IR (film): ν˜ ϭ 3076, 2997, 2928, 2856, 1737, 1640, 1435,
Dimethyl Spiro{cyclopropane-1,4Ј-[2Ј-phenyl-3Ј-vinylbicyclo[4.3.0]-
nona-1Ј(6Ј),2Ј-diene-8Ј,8Ј-dicarboxylate]} (21-Ph): According to
GP2, Pd(OAc)2 (11.2 mg, 49.9 µmol, 10 mol %), PPh3 (39.3 mg,
150 µmol, 30 mol %), K2CO3 (138 mg, 999 µmol) and 2-(2Ј-
bromoallyl)-2-(3ЈЈ-phenyl-2ЈЈ-propynyl)malonate (5-Ph, 183 mg,
501 µmol) were stirred in DMF (5 mL) with bicyclopropylidene
(80.0 mg, 998 µmol) at 110 °C for 12 h. Column chromatography
on silica gel (100 g, 3 ϫ 30 cm, pentane/diethyl ether, 10:1, Rf ϭ
0.50) yielded 21-Ph (89 mg, 49%) as a yellowish oil, which solidi-
fied in the freezer to give an amorphous solid. IR (film): ν˜ ϭ 3080,
3001, 2953, 2844, 1735, 1601, 1491, 1435, 1258, 1199, 1170, 1072,
1252, 1199, 1164, 1072, 994, 912, 819, 734, 646 cmϪ1 1H NMR
.
(250 MHz, CDCl3): δ ϭ 0.38 (mc, 2 H, Cpr-H), 0.72 (mc, 2 H, Cpr-
H), 1.23Ϫ1.49 (m, 6 H, 2ЈЈ-H, 3ЈЈ-H, 4ЈЈ-H), 1.97Ϫ2.20 (m, 4 H,
1ЈЈ-H, 5ЈЈ-H), 2.02 (br. s, 2 H, 5Ј-H), 3.02 (br. s, 2 H, 7Ј-H), 3.16
(br. s, 2 H, 9Ј-H), 3.73 (s, 6 H, OCH3), 4.84Ϫ5.04 (m, 3 H, 7ЈЈ-H,
CϭCHHvinyl), 5.14 (dd, 3J ϭ 11.4, 2J ϭ 2.4 Hz, 1 H, CϭCHHvinyl),
5.69Ϫ5.87 (m, 1 H, 6ЈЈ-H), 5.94 (dd, 3J ϭ 17.6, 3J ϭ 11.4 Hz, 1 H,
HCϭCHHvinyl) ppm. 13C NMR (62.9 MHz, CDCl3, DEPT): δ ϭ
13.41 (Ϫ, 2 C, Cpr-C), 18.22 (Cquat, Cpr-C), 28.65 (Ϫ, C-3ЈЈ), 29.07
(Ϫ, C-2ЈЈ), 30.34 (Ϫ, C-4ЈЈ), 30.51 (Ϫ, C-1ЈЈ), 33.69 (Ϫ, C-5ЈЈ),
34.29 (Ϫ, C-5Ј), 40.35 (Ϫ, C-9Ј), 43.26 (Ϫ, C-7Ј), 52.75 (ϩ, 2 C,
OCH3), 58.39 (Cquat, C-8Ј), 114.14 (Ϫ, C-7ЈЈ), 116.37 (Ϫ, Cϭ
912, 733, 702, 649 cmϪ1 1H NMR (250 MHz, CDCl3): δ ϭ 0.56
.
(mc, 2 H, Cpr-H), 0.93 (mc, 2 H, Cpr-H), 2.18 (br. s, 2 H, 5Ј-H),
2.85 (mc, 2 H, 7Ј-H), 3.10 (br. s, 2 H, 9Ј-H), 3.70 (s, 6 H, OCH3),
4.77 (dd, 3J ϭ 17.8, 2J ϭ 2.0 Hz, 1 H, CϭCH2), 4.89 (dd, 3J ϭ
11.6, 2J ϭ 2.0 Hz, 1 H, CϭCH2), 5.82 (dd, 3J ϭ 17.8, 3J ϭ 11.6 Hz,
1 H, HCϭCH2), 7.06Ϫ7.46 (m, 5 H, aryl-H) ppm. 13C NMR
(62.9 MHz, CDCl3, DEPT): δ ϭ 14.27 (Ϫ, 2 C, Cpr-C), 18.55
(Cquat, Cpr-C), 36.16 (Ϫ, C-5Ј), 41.45 (Ϫ, C-9Ј), 43.58 (Ϫ, C-7Ј),
52.80 (ϩ, 2 C, OCH3), 58.12 (Cquat, C-8Ј), 118.75 (Ϫ, CϭCH2),
126.27 (ϩ, aryl-C), 127.83 (ϩ, 2 C, aryl-C), 129.47 (ϩ, 2 C, aryl-
C), 130.902 (Cquat, C-6Ј), 132.05 (Cquat, C-3Ј), 132.79 (ϩ, CϭCH2),
133.87 (Cquat, aryl-C), 135.56 (Cquat, C-2Ј), 139.94 (Cquat, C-1Ј),
172.62 (Cquat, 2 C, CϭO) ppm. MS (200 eV, DCI, NH3): m/z (%) ϭ
746 (7) [2 M ϩ NH4ϩ], 382 (75) [M ϩ NH4ϩ], 365 (100) [M ϩ Hϩ].
C23H24O4 (364.4): calcd. C 75.80, H 6.64; found C 76.13, H 6.33.
CH2(vinyl)), 130.79 (Cquat, C-6Ј), 131.23 (Cquat, C-2Ј), 132.92 (Cquat
,
C-3Ј), 132.92 (ϩ, CϭCH2(vinyl)), 134.22 (Cquat, C-1Ј), 139.00 (ϩ, C-
6ЈЈ), 172.61 (Cquat, 2 C, CϭO) ppm. MS (EI, 70 eV): m/z (%) ϭ
384 (60) [Mϩ], 369 (33) [Mϩ Ϫ CH3], 324 (61) [Mϩ Ϫ HCO2CH3],
265 (50), 241 (51), 227 (100), 183 (77), 167 (74), 153 (61). C24H32O4
(384.5): calcd. C 74.97, H 8.39; found C 74.73, H 8.11.
Spiro[cyclopropane-1,5Ј-(7Ј-phenyl-6Ј-vinyl-1Ј,3Ј,4Ј,5Ј-tetrahydroiso-
benzofuran)] (22-Ph): According to GP2, Pd(OAc)2 (11.2 mg,
49.9 µmol, 10 mol %), PPh3 (39.3 mg, 150 µmol, 30 mol %), K2CO3
(138 mg, 999 µmol) and [3Ј-(2ЈЈ-bromoallyloxy)-1Ј-propynyl]ben-
zene (9-Ph, 126 mg, 502 µmol) were stirred in DMF (5 mL) with
bicyclopropylidene (80.0 mg, 998 µmol) at 110 °C for 11 h. Column
chromatography on silica gel [100 g, 3 ϫ 30 cm, pentane/diethyl
ether, 20:1, Rf ϭ 0.80 (pentane/diethyl ether, 10:1)] yielded 22-Ph
(90 mg, 72%) as a yellow oil. IR (film): ν˜ ϭ 3060, 2934, 2869, 1728,
Dimethyl
Spiro{cyclopropane-1,4Ј-[2Ј-(tert-butyldimethylsilyl)-3Ј-
(21-
vinylbicyclo[4.3.0]nona-1Ј(6Ј),2Ј-diene-8Ј,8Ј-dicarboxylate]}
TBDMS): According to GP2, Pd(OAc)2 (11.2 mg, 49.9 µmol,
10 mol %), PPh3 (39.3 mg, 150 µmol, 30 mol %), K2CO3 (138 mg,
999 µmol) and dimethyl 2-(2Ј-bromoallyl)-2-[3ЈЈ-tert-butyl(dimeth-
yl)silyl-2ЈЈ-propynyl]malonate (5-TBDMS, 202 mg, 501 µmol) were
stirred in DMF (5 mL) with bicyclopropylidene (80.0 mg,
998 µmol) at 110 °C for 11 h. Column chromatography on silica
gel (100 g, 3 ϫ 30 cm, pentane/diethyl ether, 10:1, Rf ϭ 0.40)
yielded 21-TBDMS (131 mg, 65%) as a pale yellow oil. IR (film):
ν˜ ϭ 2955, 2932, 2887, 2858, 1737, 1436, 1362, 1265, 1202, 1171,
1
1600, 1493, 1443, 1045, 910, 734, 648 cmϪ1. H NMR (250 MHz,
CDCl3): δ ϭ 0.61 (mc, 2 H, Cpr-H), 0.98 (mc, 2 H, Cpr-H), 2.22
(br. s, 2 H, 4Ј-H), 4.41Ϫ4.49 (m, 2 H, 3Ј-H), 4.63Ϫ4.76 (m, 4 H,
3
2
1Ј-H), 4.81 (dd, J ϭ 17.4, J ϭ 2.0 Hz, 1 H, CϭCH2), 4.96 (dd,
3J ϭ 11.3, J ϭ 2.0 Hz, 1 H, CϭCH2), 5.89 (dd, J ϭ 17.4, J ϭ
11.3 Hz, 1 H, HCϭCH2), 7.03Ϫ7.09 (m, 2 H, aryl-H), 7.11Ϫ7.31
(m, 3 H, aryl-H) ppm. 13C NMR (62.9 MHz, CDCl3, DEPT): δ ϭ
14.25 (Ϫ, 2 C, Cpr-C), 18.63 (Cquat, Cpr-C), 33.01 (Ϫ, C-4Ј), 75.36
(Ϫ, C-1Ј), 76.52 (Ϫ, C-3Ј), 119.53 (Ϫ, CϭCH2), 126.54 (ϩ, aryl-
2
3
3
1
1069, 837, 776, 737, 703, 677 cmϪ1. H NMR (250 MHz, CDCl3):
C), 127.54 (ϩ, 2 C, aryl-C), 128.91 (ϩ, 2 C, aryl-C), 129.82 (Cquat
C-6Ј*), 131.61 (Cquat, C-3Ј*), 132.36 (ϩ, HCϭCH2), 136.29 (Cquat
C-7aЈ), 139.46 (Cquat, aryl-C) ppm. Signal of C-7Ј not detected. MS
(EI, 70 eV): m/z (%) ϭ 250 (38) [Mϩ], 220 (100) [Mϩ Ϫ C2H6], 205
(34), 192 (90), 178 (87), 165 (60), 115 (24). HRMS: calcd. for
C18H18O: 250.1358 (correct mass).
,
,
δ ϭ 0.17 [s, 6 H, Si(CH3)2], 0.44 (mc, 2 H, Cpr-H), 0.73 (mc, 2 H,
Cpr-H), 0.88 [s, 9 H, C(CH3)3], 1.96 (br. s, 2 H, 5Ј-H), 2.99 (br. s,
2 H, 7Ј-H), 3.22 (mc, 2 H, 9Ј-H), 3.73 (s, 6 H, OCH3), 4.91 (dd,
2
3
2
3J ϭ 17.4, J ϭ 2.4 Hz, 1 H, CϭCH2), 5.10 (dd, J ϭ 10.9, J ϭ
2.4 Hz, 1 H, CϭCH2), 6.23 (dd, 3J ϭ 17.4, 3J ϭ 10.9 Hz, 1 H,
HCϭCH2) ppm. 13C NMR (62.9 MHz, CDCl3, DEPT): δ ϭ 0.47
[ϩ, 2 C, Si(CH3)2], 13.08 (Ϫ, 2 C, Cpr-C), 18.41 [Cquat, C(CH3)3], Spiro{cyclopropane-1,5Ј-[7Ј-(tert-butyldimethylsilyl)-6Ј-vinyl-
19.35 (Cquat, Cpr-C), 27.56 [ϩ, 3 C, C(CH3)3], 34.88 (Ϫ, C-5Ј), 1Ј,3Ј,4Ј,5Ј-tetrahydroisobenzofuran]} (22-TBDMS): According to
42.79 (Ϫ, C-9Ј), 43.90 (Ϫ, C-7Ј), 52.73 (ϩ, 2 C, OCH3), 58.64 GP2, Pd(OAc)2 (11.2 mg, 49.9 µmol, 10 mol %), PPh3 (39.3 mg,
590
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 582Ϫ592