Copper-catalyzed carbonylative catenation of olefins: Direct synthesis of γ-boryl esters

Summary

Carbonylation reactions have become an important part of contemporary organic chemistry, as they represent powerful methodologies for typically facilitating access to the core (CO)_n or (CH₂)_m building blocks with carbon monoxide as the C1 source. Here, we report a copper-catalyzed carbonylative catenation and borylation of olefins under mild conditions showing for the first time. In this procedure, two molecules of CO were regarded as the –CH₂CO– structure source. Direct carbonylative borofunctionalization of various β-substituted styrenes and alcohols leads to γ-boryl esters in high diastereomeric selectivity. Further synthetic transformations of the obtained γ-boryl esters have been developed as well. Mechanistic studies revealed that the –CH₂CO– block was derived from two molecules of CO, and a possible reaction pathway was proposed.