Copper-Catalyzed Hydroalumination of Allenes with Diisobutylaluminum Hydride: Synthesis of Allylic Ketones with α-Quaternary Centers via Tandem Allylation/Oppenauer Oxidation.

An efficient and straightforward approach to allylaluminum reagent synthesis through Cu-catalyzed hydroalumination of readily accessible allenes with diisobutylaluminum hydride is described. The N-heterocyclic carbene-based copper complex promotes hydride addition to various functionalized allenes under mild reaction conditions. The catalytic reaction is applied to a highly selective one-pot synthesis of allylic ketones with α-tertiary and α-quaternary centers through tandem nucleophilic addition of in situ-generated allylaluminums to aldehydes/Oppenauer oxidation.