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A Nitrone Dipolar Cycloaddition Strategy toward an Enantioselective Synthesis of Massadine.

ABSTRACT: An enantioselective route to the C,D-bicycle of massadine is reported. Enantiopure intermediates were generated by a single stereoselective reduction using the Corey-Bakshi-Shibata reagent. This initial stereoinduction was translated into the five contiguous stereocenters of the massadine D-ring by a synthetic route that features a diastereoselective and stereospecific Ireland-Claisen rearrangement of a trianionic enolate followed by a diastereoselective nitrone dipolar cycloaddition of a highly electron-poor oxime.

SUBMITTER: Cannon JS

PROVIDER: S-EPMC6674976 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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A Nitrone Dipolar Cycloaddition Strategy toward an Enantioselective Synthesis of Massadine.

Cannon Jeffrey S JS

Organic letters 20180613 13

An enantioselective route to the C,D-bicycle of massadine is reported. Enantiopure intermediates were generated by a single stereoselective reduction using the Corey-Bakshi-Shibata reagent. This initial stereoinduction was translated into the five contiguous stereocenters of the massadine D-ring by a synthetic route that features a diastereoselective and stereospecific Ireland-Claisen rearrangement of a trianionic enolate followed by a diastereoselective nitrone dipolar cycloaddition of a highly ...[more]

PMID: 29897770

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