Chemoselective nucleophilic arylation and single-step oxidative esterification of aldehydes using siloxanes and a palladium-phosphinous acid as a reaction switch.

Aldehydes and siloxanes form methyl esters in a single step through mild oxidative esterification in the presence of a palladium catalyst or, alternatively, afford secondary alcohols via TBAF-promoted arylation in the absence of a catalyst at increased temperatures under otherwise identical reaction conditions.