Angewandte
Chemie
d = 8.06 (br s, 1H), 7.60 (d, J = 2.0 Hz, 1H), 7.24 (d, J = 8.6 Hz, 1H),
7.17 (t, J = 2.9 Hz, 1H), 7.13(dd, J = 2.0, 8.6 Hz, 1H), 6.48–6.47 ppm
(m, 1H); 13C NMR (100 MHz, CDCl3): 134.0, 128.8, 125.5, 125.3,
122.2, 120.0, 112.0, 102.3ppm; HRMS (EI) m/z calcd for C8H6ClN
[M+]: 151.0189, found: 151.0183.
[8] B. C. Laguzza, B. Ganem, Tetrahedron Lett. 1981, 22, 1483–
1486.
[9] H. Werner, J. Wolf, A. Hohn, J. Organomet. Chem. 1985, 287,
395 – 407.
[10] a) H. Werner, J. Wolf, F. Garcia Alonso, J. Organomet. Chem.
1987, 336, 397 – 411; b) D. B. Grotjahn, X. Zeng, A. L. Cooksy, J.
Am. Chem. Soc. 2006, 128, 2798 – 2799; c) Y. Wakatsuki, J.
Organomet. Chem. 2004, 689, 4092 – 4109.
Received: October 13, 2006
Published online: February 7, 2007
[11] a) K. Iritani, S. Matsubara, K. Utimoto, Tetrahedron Lett. 1988,
29, 1799 – 1802; b) A. Arcadi, S. Cacchi, F. Marinelli, Tetrahe-
dron Lett. 1989, 30, 2581 – 2584; c) S. Cacchi, V. Carnicelli, F.
Marinelli, J. Organomet. Chem. 1994, 475, 289 – 296.
[12] A. Arcadi, G. Bianchi, F. Marinelli, Synthesis 2004, 4, 610 – 618.
[13] N. Sakai, K. Annaka, T. Konakahara, Org. Lett. 2004, 6, 1527 –
1530.
Keywords: alkynes · atom economy · cyclization ·
homogeneous catalysis · rhodium
.
[1] a) B. M. Trost, Science 1991, 254, 1471 – 1477; b) B. M. Trost,
Angew. Chem. 1995, 107, 285 – 307; Angew. Chem. Int. Ed. Engl.
1995, 34, 259 – 281.
[2] a) B. M. Trost, Acc. Chem. Res. 2002, 35, 695 – 705; b) B. M.
Trost, F. D. Toste, A. B. Pinkerton, Chem. Rev. 2001, 101, 2067 –
2096.
[3] For reviews of vinylidenes in catalysis, see: a) C. Bruneau, P. H.
Dixneuf, Acc. Chem. Res. 1999, 32, 311 – 323; b) C. Bruneau,
P. H. Dixneuf, Angew. Chem. 2006, 118, 2232 – 2260; Angew.
Chem. Int. Ed. 2006, 45, 2176 – 2203.
[4] a) B. M. Trost, G. Dyker, R. J. Kulawiec, J. Am. Chem. Soc. 1990,
112, 7809 – 7811; b) B. M. Trost, R. J. Kulawiec, J. Am. Chem.
Soc. 1992, 114, 5579 – 5584; c) B. M. Trost, R. J. Kulawiec, A.
Hammes, Tetrahedron Lett. 1993, 34, 587 – 590; d) B. M. Trost,
J. A. Flygare, J. Org. Chem. 1994, 59, 1078 – 1082.
[5] a) B. M. Trost, Y. H. Rhee, J. Am. Chem. Soc. 2002, 124, 2528 –
2533; b) B. M. Trost, Y. H. Rhee, J. Am. Chem. Soc. 2003, 125,
7482 – 7483.
[14] D. E. Rudisill, J. K. Stille, J. Org. Chem. 1989, 54, 5856 – 5866.
[15] a) K. Hiroya, S. Itoh, M. Ozawa, Y. Kanamori, T. Sakamoto,
Tetrahedron Lett. 2002, 43, 1277 – 1280; b) K. Hiroya, S. Itoh, T.
Sakamoto, J. Org. Chem. 2004, 69, 1126 – 1136; c) K. Hiroya, S.
Itoh, T. Sakamoto, Tetrahedron 2005, 61, 10958 – 10964.
[16] T. Kondo, T. Okada, T. Suzuki, T. Mitsudo, J. Organomet. Chem.
2001, 622, 149 – 154.
[17] Homolytic bond strengths: C6H5NH H: 88.0 kcalmolꢀ1
;
ꢀ
C6H5O H: 86.5 kcalmolꢀ1; see: D. F. McMillen, D. M. Golden,
Annu. Rev. Phys. Chem. 1982, 33, 493– 532.
ꢀ
[18] G. R. Humphrey, J. T. Kuethe, Chem. Rev. 2006, 106, 2875 – 2911.
[19] For carbon nucleophiles, see: a) F. E. McDonald, T. C. Olson,
Tetrahedron Lett. 1997, 38, 7691 – 7692; b) K. Maeyama, N.
Iwasawa, J. Am. Chem. Soc. 1998, 120, 1928 – 1929; c) N.
Iwasawa, T. Miura, K. Kiyota, H. Kusama, K. Lee, P. H. Lee,
Org. Lett. 2002, 4, 4463– 4466; for nitrogen nucleophiles, see:
F. E. McDonald, A. K. Chatterjee, Tetrahedron Lett. 1997, 38,
7687 – 7690.
[6] F. E. McDonald, M. M. Gleason, J. Am. Chem. Soc. 1996, 118,
6648 – 6659.
[7] S. Kajigaeshi, T. Kakinami, H. Yamasaki, S. Fujisaki, T.
Okamoto, Bull. Chem. Soc. Jpn. 1988, 61, 600 – 602.
Angew. Chem. Int. Ed. 2007, 46, 2074 –2077
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