Ir(iii)-catalyzed ortho C-H alkylations of (hetero)aromatic aldehydes using alkyl boron reagents.

Abstract

Transition-metal-catalyzed C-H alkylation reactions directed by aldehydes or ketones have been largely restricted to electronically activated alkenes. Herein, we report a general protocol for the Ir(iii)-catalyzed ortho C-H alkylations of (hetero)aromatic aldehydes using alkyl boron reagents as the coupling partner. Featuring aniline as an inexpensive catalytic ligand, the method was compatible with a wide variety of benzaldehydes, heterocyclic aldehydes, potassium alkyltrifluoroborates as well as a few α,β-unsaturated aldehydes. An X-ray crystal structure of a benzaldehyde ortho C-H iridation intermediate was also successfully obtained.