Rhodium‐Catalyzed Benzylic Addition Reactions of Alkylarenes to Michael Acceptors

Abstract The use of alkylarenes as nucleophile precursors in benzylic addition is challenging because the benzylic hydrogen atoms of these compounds are inert to deprotonation. Herein, we report Rh‐catalyzed benzylic addition of alkylarenes to Michael acceptors for the formation of C(sp 3 )−C(sp 3 ) bonds. The catalyst is proposed to activate the aromatic ring via η 6 ‐coordination, dramatically facilitating deprotonation of the unactivated benzylic C−H bond and addition of the resulting carbanion to the α,β‐unsaturated double bond in the absence of bases. Notably, this byproduct‐free method provides an access to all‐carbon quaternary centers through the development of ligands.