An enantioselective total synthesis of (+)- and (-)-saudin. Determination of the absolute configuration. |
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Authors: | Robert K Boeckman Maria del Rosario Rico Ferreira Lorna H Mitchell Pengcheng Shao |
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Institution: | Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, USA. |
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Abstract: | A short efficient enantioselective synthesis of both (+)- and (-)-saudin, a naturally occurring hypoglycemic diterpene, is described. This synthesis establishes the absolute configuration of natural (-)-saudin for the first time. The key steps include the enantioselective construction of a dimethyl Hagemann's ester by an asymmetric Michael reaction and establishment of the key 1,3 disposed quaternary centers by means of a novel Ti(IV) promoted Claisen rearrangement. The assembly of the polycyclic ketal skeleton was likely under kinetic control proceeding via formation of the C1oxygen-C7 bond through an oxonium ion intermediate in the final stage. |
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