The construction of enantiopure quaternary carbon center is a challenging task in asymmetric catalysis. Chiral α,α -disubstituted aldehydes have long been applied as an electron acceptor for the creation of continuous stereogenic centers. However, nucleophilic substitution of α, α -disubstituted aldehydes is still limited due to the lack of reactivity and steric hindrance. Herein, we reported a direct enantioselective allylic alkylation by merging asymmetric enamine catalysis and Pd/Ir catalysis. This cooperative catalysis afforded full stereocontrol of up to two stereogenic centers with excellent stereoselectivity and the corresponding chiral allylic aldehyde products were isolated in good yields. Control experiments and NMR studies revealed that the formation of enamine between the chiral amino catalyst and the aldehyde substrates undergoes a kinetic resolution.

Highly enantioselective allylic alkylation of α, α-disubstituted aldehyde by chiral amino/organometallic cooperative catalysis

ACS Spring 2022

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