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Formal [4+2] Cycloadditions of Anhydrides and ⍺,β-Unsaturated N-Tosyl Ketimines

Abstract

Herein is described a method for the diastereoselective synthesis of highly-substituted β-enamino ketones from anhydrides and ketone-derived imines. Cyclic, enolizable anhydrides undergo a base-promoted conjugate addition reaction with ⍺,β-unsaturated N-tosyl ketimines, followed by an intramolecular acylation to give formal [4+2] cycloaddition products. The carboxylic acid-containing products are formed in modest selectivity for the cis-diastereomer and can be fully epimerized to the trans-diastereomer upon esterification.

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