Abstract

It has been established that a cationic rhodium(I)/H8-binap or binap complex catalyzes two different modes of cyclization of γ-alkynyl aldehydes with carboxylic acid anhydrides to give cyclic aldehyde gem-dicarboxylates and cyclic alkenyl esters through cleavage of the carboxylic acid anhydride C–O bond. The reaction of a terminal γ-alkynyl aldehyde with diethyl pyrocarbonate afforded a cyclic allylic carbonate with a high ee value.

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