Branched‐Selective Direct α‐Alkylation of Cyclic Ketones with Simple Alkenes

Herein, we describe an intermolecular direct branched-selective α-alkylation of cyclic ketones with simple alkenes as the alkylation agents. Through an enamine-transition metal cooperative catalysis mode, the α-alkylation is realized in an atom- and step-economic manner with excellent branched selectivity for preparing β-branched ketones. Employment of a pair of bulky Brønsted acid and base as additives is responsible for enhanced efficiency. Promising enantioselectivity (74 % ee) has been obtained. Experimental and computational mechanistic studies suggest that a pathway through alkene migratory insertion into the Ir-C bond followed by C-H reductive elimination is involved for the high branched selectivity.