M. Shi and J.-M. Lu
pressure and the residue was purified by a flash column chromatography
under reduced pressure and the residue was purified by a flash column
chromatography.
MS (EI): m/z (%): 536 (25.16) [M+], 302 (100), 303 (64), 77 (29), 379
(26.1), 304 (25.9), 189 (25.22), 182 (25.0); HRMS (EI): m/z: calcd for
C36H25Br: 536.1140; found: 536.1147; (anti-isomer): White solid; m.p.
1
200–2018C; H NMR (CDCl3, 300 MHz, TMS): d = 5.30 (s, 1H), 6.26 (s,
General procedure for the transformation of 6 to 22 in the presence of
TfOH: Under an argon atmosphere, allenol 6 (0.05 mmol) and DCE
(1.0 mL) were added into a Schlenk tube, then TfOH (10 mol%) was
added. The reaction mixture was stirred at room temperature for 0.5 h,
then the solvent was removed under reduced pressure and the residue
was purified by a flash column chromatography.
1H), 6.74 (d, J=7.8 Hz, 1H, Ar), 7.05–7.53 (m, 19H, Ar), 7.62 (d, J=
7.5 Hz, 1H, Ar), 7.86 (d, J=8.1 Hz, 1H, Ar), 8.31 ppm (d, J=8.4 Hz,
1H, Ar); 13C NMR (CDCl3, 75 MHz, TMS): d = 46.7, 49.1, 120.9, 124.3,
125.5, 126.3, 126.4, 126.8, 127.2, 127.5, 128.2, 128.4, 128.7, 128.8, 130.1,
131.0, 131.3, 131.9, 132.6, 136.0, 138.0, 138.6, 139.2, 140.6, 143.3,
144.5 ppm; IR (CH2Cl2): n˜ = 3059, 3023, 2924, 2852, 1946, 1898, 1594,
1574, 1487, 1452, 1403, 1385, 1264, 1101, 1072, 1011, 936, 898, 757, 739,
703 cmÀ1; MS (EI): m/z (%): 536 (27) [M+], 302 (100), 303 (65), 380 (39),
379 (31), 538 (28.0), 189 (27.6), 182 (26); HRMS (EI): m/z: calcd for
C36H25Br: 536.1140; found: 536.1153.
Compound 8a: Yellow oil; 1H NMR (CDCl3, 300 MHz, TMS): d = 1.94
(brs, 1H, OH), 5.00 (s, 1H), 5.38 (s, 1H), 5.50 (d, J=1.2 Hz, 1H), 6.32 (s,
1H), 6.60 (d, J=1.2 Hz, 1H), 6.97–7.01 (m, 2H, Ar), 7.15–7.35 ppm (m,
18H, Ar); 13C NMR (CDCl3, 75 MHz, TMS): d
= 75.1, 116.8, 126.4,
126.48, 126.52, 127.4, 127.6, 127.8, 127.9, 128.0, 128.1, 128.3, 129.8, 140.4,
141.1, 142.9, 143.6, 143.9, 144.3 ppm; IR (CH2Cl2): n˜ = 3566, 3446, 3057,
3026, 2925, 1945, 1878, 1800, 1599, 1573, 1492, 1444, 1380, 1181, 1075,
1028, 899, 773, 762, 700 cmÀ1; MS (EI) m/z (%): 396 (100) [M+À18], 397
(30), 305 (21), 317 (15), 318 (14.1), 303 (13.8), 319 (13), 241 (12); HRMS
(EI): m/z: calcd for C31H26: 414.1984; found: 414.1984.
Compound 11a: White solid; m.p. 138–1398C; 1H NMR (CDCl3,
300 MHz, TMS): d = 2.33 (s, 3H, CH3), 4.79 (d, J=7.2 Hz, 1H), 5.10 (d,
J=7.2 Hz, 1H), 5.34 (s, 1H), 5.51 (d, J=0.9 Hz, 1H), 6.20 (s, 1H), 6.56
(s, 1H), 6.74–6.82 (m, 4H, Ar), 7.05–7.16 (m, 10H, Ar), 7.22–7.26 (m,
5H, Ar), 7.35–7.41 ppm (m, 5H, Ar); 13C NMR (CDCl3, 75 MHz, TMS):
d = 21.4, 60.6, 117.2, 126.1, 126.5, 127.10, 127.13, 127.4, 127.47, 127.54,
127.78, 128.81, 127.9, 128.2, 128.4, 129.2, 129.9, 130.2, 137.3, 139.7, 139.8,
140.7, 142.8, 143.0, 143.8, 143.9 ppm; IR (CH2Cl2): n˜ = 3274, 3057, 3028,
2924, 1945, 1885, 1797, 1598, 1573, 1493, 1444, 1329, 1160, 1094, 1029,
900, 813, 774, 699 cmÀ1; MS (EI): m/z (%): 567 (5) [M+], 396 (100), 260
(46), 412 (42), 397 (31), 307 (29), 411 (26), 319 (17), 306 (15); HRMS
(EI): m/z: calcd for C38H33NO2S: 567.2232; found: 567.2233.
1
Compound 22a: Red solid; m.p. 177–1788C; H NMR (CDCl3, 300 MHz,
TMS): d = 6.25 (s, 1H), 6.32 (d, J=7.8 Hz, 1H, Ar), 6.70–6.81 (m, 5H,
Ar), 6.94–6.96 (m, 2H, Ar), 7.04–7.36ppm (m, 21H, Ar); 13C NMR
(CDCl3, 75 MHz, TMS): d
= 119.6, 123.0, 124.8, 126.4, 126.7, 127.0,
127.3, 127.52, 127.54, 127.7, 128.07, 128.11, 128.2, 128.5, 128.87, 128.90,
130.7, 131.9, 135.25, 135.32, 137.7, 138.6, 140.5, 141.8, 142.67, 142.70,
143.0, 143.37, 143.43, 148.3 ppm; IR (CH2Cl2): n˜
= 3055, 3025, 2925,
1936, 1869, 1799, 1595, 1489, 1441, 1352, 1327, 1178, 1156, 1074, 1029,
786, 760, 739, 697 cmÀ1; MS (EI): m/z (%): 534 (100) [M+], 367 (76), 535
(45), 379 (34), 189 (28), 368 (25), 165 (19), 289 (18); elemental analysis
calcd (%) for C42H30 (3/5CH2Cl2): C 87.37, H 5.37; found: C 87.53, H
5.61.
Acknowledgements
1
Compound 12a: Yellow oil; H NMR (CDCl3, 300 MHz, TMS): d = 2.08
We thank the Shanghai Municipal Committee of Science and Technology
(06XD14005, 08dj1400100-2), National Basic Research Program of China
AHCTUNGERTG(NNUN 973)-2009CB825300, and the National Natural Science Foundation of
China for financial support (20472096, 20872162, 20672127, 20821002 and
20732008).
(s, 3H, CH3), 2.34 (d, J=1.2 Hz, 3H, CH3), 2.55–2.68 (m, 4H), 6.02 (d,
J=1.2 Hz, 1H), 7.19–7.37 (m, 9H, Ar), 7.43–7.50 ppm (m, 6H, Ar);
13C NMR (CDCl3, 75 MHz, TMS): d = 18.7, 30.1, 34.9, 40.4, 49.5, 84.9,
98.7, 106.6, 125.3, 126.6, 127.2, 128.0, 128.3, 128.4, 140.8, 144.9, 147.9,
208.4 ppm; IR (CH2Cl2): n˜ = 3082, 3057, 3024, 2924, 1715, 1597, 1493,
1446, 1363, 1160, 1029, 757, 699 cmÀ1; MS (EI): m/z (%): 378 (5) [M+],
229 (100), 320 (85), 305 (81), 307 (43), 215 (34.6), 291 (34.5), 292 (33),
228 (27); HRMS (EI): m/z: calcd for C28H26O: 378.1984; found: 378.1985.
[2] a) W. I. I. Bakker, P. L. Wong, V. Snieckus, J. M. Warrington, L. Bar-
riault in e-EROS (Ed.: L. A. Paquette), Wiley, New York, 2004;
1
Compound 15a: Yellow oil; H NMR (CDCl3, 300 MHz, TMS): d = 2.08
(s, 3H, CH3), 2.34 (d, J=1.2 Hz, 3H, CH3), 2.55–2.68 (m, 4H), 6.02 (d,
J=1.2 Hz, 1H), 7.19–7.37 (m, 9H, Ar), 7.43–7.50 ppm (m, 6H, Ar);
13C NMR (CDCl3, 75 MHz, TMS): d = 18.7, 30.1, 34.9, 40.4, 49.5, 84.9,
98.7, 106.6, 125.3, 126.6, 127.2, 128.0, 128.3, 128.4, 140.8, 144.9, 147.9,
208.4 ppm; IR (CH2Cl2): n˜ = 3082, 3057, 3024, 2924, 1715, 1597, 1493,
1446, 1363, 1160, 1029, 757, 699 cmÀ1; MS (EI): m/z (%): 378 (5) [M+],
229 (100), 320 (85), 305 (81), 307 (43), 215 (34.6), 291 (34.5), 292 (33),
228 (27); HRMS (EI): m/z: calcd for C28H26O: 378.1984; found: 378.1985.
Compound 17a: White solid; m.p. 83–848C; 1H NMR (CDCl3, 300 MHz,
TMS): d = 2.01 (t, J=2.4 Hz, 1H), 2.36 (d, J=0.9 Hz, 3H, CH3), 3.22 (d,
J=2.4 Hz, 2H), 6.03 (d, J=0.9 Hz, 1H), 7.20–7.34 (m, 9H, Ar), 7.42–
7.51 ppm (m, 6H, Ar); 13C NMR (CDCl3, 75 MHz, TMS): d = 18.7, 32.9,
49.9, 71.3, 81.0, 84.3, 98.5, 106.7, 125.4, 126.9, 127.4, 127.9, 128.2, 128.3,
140.9, 144.1, 148.3 ppm; IR (CH2Cl2): n˜ = 3295, 3058, 3029, 2916, 1946,
1872, 1799, 1597, 1492, 1446, 1378, 1267, 1185, 1071, 1030, 848, 756, 697,
653 cmÀ1; MS (EI): m/z (%): 346 (8) [M+], 307 (100), 229 (74), 308 (29),
215 (26), 228 (24), 291 (19), 129 (19), 128 (15); HRMS (EI): m/z: calcd
for C27H22: 346.1722; found: 345.1720.
ences therein; b) D. Bellus, B. Klingert, R. W. Lang, A. Rihs, J. Or-
[4] For the synthesis of vinylidenecyclopropanes, please, see: a) K. Isa-
M. S. Baird, J. Chem. Soc. Perkin Trans. 1 1994, 1547–1548. For
some other papers related to vinylidenecyclopropanes: c) H. Maeda,
4556. For a recent review, see: e) H. Maeda, K. Mizuno, J. Synth.
Org. Chem. Jpn. 2004, 62, 1014–1025.
drick, J. A. Hardie, M. Jones, J. Org. Chem. 1971, 36, 3061–3062;
d) H. Sugita, K. Mizuno, T. Saito, K. Isagawa, Y. Otsuji, Tetrahedron
T. Hirai, H. Maeda, Y. Otsuji, M. Yasuda, M. Hashiguchi, K. Shima,
Compound 21a (syn-isomer): White solid; m.p. 194–1968C; 1H NMR
(CDCl3, 300 MHz, TMS): d = 5.48 (s, 1H), 6.13 (s, 1H), 6.77 (d, J=
8.7 Hz, 2H, Ar), 6.95–7.06 (m, 7H, Ar), 7.26–7.76 (m, 11H, Ar), 7.85 (d,
J=8.4 Hz, 1H, Ar), 7.93 (d, J=8.7 Hz, 1H, Ar), 8.08 ppm (d, J=8.4 Hz,
1H, Ar); 13C NMR (CDCl3, 75 MHz, TMS): d = 46.2, 50.7, 119.9, 124.5,
125.5, 125.9, 126.5, 126.7, 126.8, 126.9, 127.4, 128.0, 128.2, 128.3, 128.4,
129.5, 130.16, 130.22, 130.7, 131.0, 132.3, 132.5, 136.2, 137.2, 139.5, 139.8,
140.6, 142.7, 143.1 ppm; IR (CH2Cl2): n˜ = 3060, 3024, 2922, 2851, 1950,
1888, 1595, 1574, 1485, 1454, 1400, 1074, 1031, 1010, 819, 753, 703 cmÀ1
;
6072
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 6065 – 6073