Unprecedented Enantioselective Intramolecular Heck-Matsuda Carbonylation Reactions

Efficient methods to construct carbon-carbon bonds have been the main aim of organic chemists. The Heck reaction, a palladium-catalyzed functionalization of olefins with electrophiles, is a powerful tool and one of the most used transformations.1 The use of arenediazonium salts as electrophiles, known as Heck-Matsuda reaction, is increasingly contributing to the synthesis of valuable compounds in a practical and efficient manner.2
In the last few years, the Correia group has been studying and improving the asymmetric intermolecular variant of this reaction and the use of many classes of olefins have been reported.2
However, the asymmetric intramolecular Heck-Matsuda reaction has never been reported, mainly due to the stability of the arenediazonium salt and the rapid formation of styrenes and/or aromatization of the intermediate. Herein we report the first examples of enantioselective intramolecular Heck-Matsuda carbonylation reactions through the capture of -alkylpalladium intermediate A with CO/alcohols and also with CO/boronic acids.