Toward the development of a general chiral auxiliary. Enantioselective alkylation and a new catalytic asymmetric addition of silyloxyfurans: application to a total synthesis of (-)-rasfonin |
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Authors: | Boeckman Robert K Pero Joseph E Boehmler Debra J |
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Affiliation: | Department of Chemistry, University of Rochester, P.O. Box 270216, Hutchison Hall, Rochester, New York 14627-0216, USA. rkb@rkbmac.chem.rochester.edu |
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Abstract: | An enantioselective total synthesis of the apoptosis-inducing natural product, (-)-rasfonin, is described. Camphor lactam-mediated asymmetric alkylation reactions enabled the installation of three stereogenic centers with >95:5 diastereoselectivity. A modified Corey-Peterson olefination was employed in the construction of the (E,E)-diene system. A highly diastereoselective, asymmetric vinylogous Mukaiyama aldol addition was conducted using a chiral cationic oxazaborolidine catalyst. The pyranone core of the natural product was prepared via a DBU-promoted rearrangement of a furanol to its corresponding pyranol with concomitant [1,4]-silyl transfer. |
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