Photoredox/palladium dual catalysis-mediated regioselective and enantioselective carbon-carbon bond formation has been achieved. Incorporation of a silicon-directing group was crucial to accomplish regioselectivity in the reaction to furnish stereogenic center bearing aliphatic substituents in a highly enantioselective fashion. Here, the well-established radical precursor 4-alkyl-1,4-dihydropyridine has been employed which when irradiated by blue LEDs, generates the desired alkyl radical which further combines with silicon-substituted π-(allyl)Pd(II) complex. The resulting complex gives access to synthetically versatile vinylsilane moiety after reductive elimination. Both steric and electronic factors directed the nucleophilic attack to the distal carbon in the π-(allyl)Pd(II) complex bearing aliphatic substituents. The present approach provides access to a vast range of enantioenriched products which are otherwise difficult to obtain by using traditional two-electron Pd-catalyzed asymmetric allylic alkylation. Moreover, the synthetically versatile vinylsilane moiety in the product provides a useful platform for further functionalization.

Regioselective asymmetric allylic alkylation by merging Pd/photoredox dual catalysis using silicon as a directing group

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