The compounds with a quaternary α-aryl aldehyde skeleton are important units in organic chemistry. Previously, the aryl group and carbonyl group are introduced in a stepwise manner. Herein, a novel route is developed to construct the quaternary α-aryl aldehydes with gem-bis­(boronates) as precursors, in which the two groups are installed simultaneously. The gem-bis­(boronates) are readily available from ketones; as a result, this methodology provides a more general strategy to produce the quaternary α-aryl aldehydes with broad scopes and synthetic convenience.

A transformation of gem-bis(boronate) compounds with different electrophiles through a tertiary boronate intermediate to concurrently introduce aldehyde and allylic groups, which provides an efficient protocol to difunctionalize ketones, was reported.

Chiral N-heterocyclic carbene (NHC), a privileged ligand for transition metals, has had a profound impact on organometallic chemistry. The monodentate and bidentate chiral carbenes have been developed significantly, while the tridentate ones have been less exploited. Herein, we designed and [a] Y.