Activator-regulated chemodivergent deoxygenative- and alkoxy-carbonylation of alcohols with boronic acids

A method for the chemodivergent deoxygenative- and alkoxy-carbonylation of alcohols with boronic acids via palladium catalysis has been developed. Manipulation of the divergent selectivities depend on simply changing the choice of activators. While a carbodiimide activator promoted the formation of ketones through deoxygenative carbonylation, selectivity for esters via alkoxy carbonylation was observed with an azo activator. Notably, in addition to the broad substrate scope, this base-free strategy enables the use of highly base-sensitive boronic acid substrates. This study contributes to the art of chemoselectivity control in carbonylation chemistry.