Asymmetric Carbenoid Allylic C─H Alkylation of α‐Olefins Using Tailored Chiral Indenyl‐Rhodium Catalysts

Abstract Alpha (α)‐olefins represent cornerstone feedstocks in the chemical industry, offering a versatile platform for enhancing molecular complexity from readily available precursors. While remarkable strides have been made in the asymmetric functionalization of olefinic double bonds, the selective activation of allylic C─H bonds remain a formidable challenge. Herein, we unveil a catalytic asymmetric allylic C─H activation of α‐olefins through carbene transfer, leveraging highly active and synthetically accessible indenyl–rhodium complexes. These complexes, featuring indenyl ligands prepared via a streamlined, one‐step Pd‐catalyzed atropisomeric Suzuki–Miyaura coupling, enable precise control over chemo‐, regio‐, and enantioselectivity. This method exhibits exceptional versatility, accommodating a diverse array of olefins, ranging from bulk industrial products to those adorned with various functional groups. A comprehensive series of experiments was conducted to illustrate the wide‐ranging applicability of the asymmetric C─H activation reaction. Mechanistic investigations elucidate critical factors governing rhodium carbenoid formation, branch selectivity, and enantioselectivity during the C─H activation process.