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Several groups have employed this method to generate libraries of five- and six-membered heterocycles and substituted pyrrolidines from cyclopropyl ketones: a) M. Lautens, W. Han, J. Am. Chem. Soc. 2002, 124, 6312-6316; b) F. Bertozzi, M. Gustafsson, R. Olsson, Org. Lett. 2002, 4, 3147-3150.
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Several groups have employed this method to generate libraries of five- and six-membered heterocycles and substituted pyrrolidines from cyclopropyl ketones: a) M. Lautens, W. Han, J. Am. Chem. Soc. 2002, 124, 6312-6316; b) F. Bertozzi, M. Gustafsson, R. Olsson, Org. Lett. 2002, 4, 3147-3150.
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12244266945
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note
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2-catalyzed ring-expansion reaction, see ref. [7a].
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33947479432
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Imine 10 was prepared from known triisopropylsilanyl propynal and allylamine. a) B. Alcaide, I. M. Rodríguez-Campos, J. Rodríguez-López, A. Rodríguez-Vicente, J. Org. Chem. 1999, 64, 5377-5387; b) M. Journet, D. Cai, L. M. DiMichele, R. D. Larsen, Tetrahedron Lett. 1998, 39, 6427-6428.
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Imine 10 was prepared from known triisopropylsilanyl propynal and allylamine. a) B. Alcaide, I. M. Rodríguez-Campos, J. Rodríguez-López, A. Rodríguez-Vicente, J. Org. Chem. 1999, 64, 5377-5387; b) M. Journet, D. Cai, L. M. DiMichele, R. D. Larsen, Tetrahedron Lett. 1998, 39, 6427-6428.
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At this stage, the various isomers of 12 can be separated by chromatography on silica gel. In parallel studies, we have converted the stereoisomers epimeric at C9 (cis/trans olefins) to spirotryprostatin B. For the purpose of clarity, in this communication we describe the synthesis from 13.
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12244254951
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note
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CCDC 196803 (14) and CCDC 196804 (21) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
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