Highly regioselective C–H carbonylation of alkenes with phenyl formate via aryl to vinyl 1,4-palladium migration

Abstract

We report herein a palladium-catalyzed C–H carbonylation of gem-disubstituted ethylenes with phenyl formate as a convenient CO surrogate through an aryl to vinyl 1,4-palladium migration, providing a wide range of β,β-diaryl substituted α,β-unsaturated esters in high efficiency and with excellent regio- and stereoselectivities. The reaction proceeds with broad substrate scope and good functional group compatibility. The present synthetic protocol provides a convenient and powerful method to directly access a key intermediate for (Z)-tamoxifen.