Communications
[7] a) I. Ninomiya, O. Yamamoto, T. Naito, Heterocycles 1977, 7,
137; b) I. Ninomiya, O. Yamamoto, T. Naito, J. Chem. Soc.
Perkin Trans. 1 1983, 2165; c) I. Ninomiya, O. Yamamoto, T.
Naito, J. Chem. Soc. Perkin Trans. 1 1983, 2171; d) M. Hanaoka,
S. Yoshida, C. Mukai, Tetrahedron Lett. 1985, 26, 5163; e) M.
Yoshida, T. Watanabe, T. Ishikawa, Tetrahedron Lett. 2002, 43,
6751.
[8] a) W. Oppolzer; K. Keller, J. Am. Chem. Soc. 1971, 93, 3836;
b) W. Oppolzer, Heterocycles 1980, 14, 1615; c) M. Cushman, T.-
C. Choong, J. T. Valko, M. P. Kolek, Tetrahedron Lett. 1980, 21,
3845; d) M. Cushman, T.-C. Choong, J. T. Valko, M. P. Kolek, J.
Org. Chem. 1980, 45, 5067.
time in natural product synthesis and thus have completed the
first enantioselective total synthesis of (+)-homochelidonine
in 14 steps. The longest linear sequence is 11 steps and the
overall yield is 15% from 4,5-dibromovertrole. Studies to find
general conditions for the desymmetrization of meso-azabi-
cycles with boronic acids and the application of this method-
ology to the synthesis of other hexahydrobenzo[c]phenan-
thridine alkaloids is currently under investigation.
Received: September 26, 2006
Published online: December 5, 2006
[9] a) M. Lautens, C. Dockendorff, Org. Lett. 2003, 5, 3695; for a
review of ring-opening reactions prior to 2003, see: b) M.
Lautens, K. Fagnou, S. Hiebert, Acc. Chem. Res. 2003, 36, 48; for
ring-opening reactions after 2003, see: c) M. Lautens, S. Hiebert,
J. Am. Chem. Soc. 2004, 126, 1437; d) P. Leong, M. Lautens, J.
Org. Chem. 2004, 69, 2194; e) Y.-h. Cho, V. Zunic, H. Senboku,
M. Olsen, M. Lautens, J. Am. Chem. Soc. 2006, 128, 6837; f) Y.-h.
Cho, A. Fayol, M. Lautens, Tetrahedron: Asymmetry 2006, 17,
416.
Keywords: alkaloids · asymmetric catalysis · polycycles ·
ring-opening reactions · total synthesis
.
[1] a) E. Schmidt, F. Selle, Arch. Pharm. 1890, 228, 441; b) J. Slavik,
Cesk. Farm. 1955, 4, 15; c) J. Slavik, L. Slavíkovµ, J. Brabenec,
Collect. Czech. Chem. Commun. 1965, 30, 3697; d) R. H. F.
Manske, Can. J. Res. Sect. B 1943, 21, 140; e) N. Takao, M.
Kamiguchi, K. Iwasa, N. Morita, Arch. Pharm. 1984, 317, 223;
f) J. Slavik, E. Taborska, H. Bochorakova, Collect. Czech. Chem.
Commun. 1994, 89, 429; g) M. Neas, J. Dostµl, I. Kejnovskµ, M.
Vorlíkovµ, J. Slavík, J. Mol. Struct. 2005, 734, 1.
[2] a) F. von Bruchhausen, H. W. Bersch, Chem. Ber. 1930, 63, 2520;
b) E. Späth, F. Kuffner, Chem. Ber. 1931, 64, 370; c) H. W.
Bersch, Arch. Pharm. 1958, 291, 491; d) E. Seoane, An. R. Soc.
Esp. Fis. Quim. Ser. B 1965, 61, 755; e) C.-Y. Chen, D. B.
MacLean, Can. J. Chem. 1967, 45, 3001; f) S. Naruto, S. Arakawa,
H. Kaneko, Tetrahedron Lett. 1968, 10, 1705; g) N. Takao, N.
Bessho, M. Kamigauchi, K. Iwasa, K. Tomita, T. Fujiwara, S.
Fugii, Tetrahedron Lett. 1979, 20, 495.
[10] A. M. Qandil, D. Ghosh, D. E. Nichols, J. Org. Chem. 1999, 64,
1407.
[11] J.-L. Gras, Y.-Y. K. W. Chang, A. Guerin, Synthesis 1985, 74.
[12] Further optimization by varying the reaction conditions with
(S)-tol-binap as the ligand was attempted. However no improve-
ment in the ee value was observed; see the Supporting Informa-
tion.
[13] C. Hermann, G. C. G. Pais, A. Geyer, S. M. Kꢀhnert, M. E.
Maier, Tetrahedron 2000, 56, 8461.
[14] R. E. Ireland, M. D. Varney, J. Org. Chem. 1986, 51, 635.
[15] B. Cao, H. Park, M. M. Joulliꢁ, J. Am. Chem. Soc. 2002, 124, 520.
[16] D. L. Boger, S. R. Brunette, R. M. Garbaccio, J. Org. Chem.
2001, 66, 5163.
[3] J. M. Probst, Ann. Pharm. 1839, 29, 113.
[17] A. S.-Y. Lee, Y.-J. Hu, S.-F. Chu, Tetrahedron 2001, 57, 2121.
[18] H. Monti, G. Lꢁandri, M. Klos-Ringuet, C. Corriol, Synth.
Commun. 1983, 13, 1021; PPTS = pyridinium p-toluenesulfo-
nate.
[4] G. Grynkiewicz, E. Chojecka-Koryn, M. Gadzikowska, A.
Chodkowska, E. Jagiello-Wójtowicz, Eur. J. Med. Chem. 2001,
36, 951.
[5] A. Panzer, A. M. Joubert, P. C. Bianchi, E. Hamel, J. C. Seegers,
Eur. J. Cell Biol. 2001, 80, 111.
[6] J. W. Nowicky, G. Manolakis, D. Meijer, V. Vatanasapt, W. J.
Brzosko, Drugs Exp. Clin. Res. 1992, 18, 1.
[19] S. K. Panday, N. Langlois, Synth. Commun. 1997, 27, 1373.
[20] R. S. Lott, V. S. Chauhan, C. H. Stammer, J. Chem. Soc. Chem.
Commun. 1979, 495.
[21] See the Supporting Information.
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