Abstract

<h2>Summary</h2> Carbonylation reactions have become an important part of contemporary organic chemistry, as they represent powerful methodologies for typically facilitating access to the core (CO)<sub>n</sub> or (CH<sub>2</sub>)<sub>m</sub> 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 –CH<sub>2</sub>CO– 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 –CH<sub>2</sub>CO– block was derived from two molecules of CO, and a possible reaction pathway was proposed.

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