One‐step Synthesis of Chiral 9,10‐Dihydrophenanthrenes via Ligand‐enabled Enantioselective Cascade β,γ‐Diarylation of Acids

Pd(II)‐catalyzed enantioselective C−H activation has emerged as a versatile platform for constructing point, axial, and planar chirality. Herein, we present an unexpected discovery of a Pd‐catalyzed enantioselective cascade β,γ‐methylene C(sp 3 )−H diarylation of free carboxylic acids using bidentate chiral mono‐protected amino thioether ligands (MPAThio), enabling one‐step synthesis of a complex chiral 9,10‐dihydrophenanthrene scaffolds with high enantioselectivity. In this process, two methylene C(sp 3 )−H bonds and three C(sp 2 )−H bonds were activated, leading to the formation of four C−C bonds and three chiral centers in one pot. A plausible catalytic pathway starts with enantioselective β,γ‐dehydrogenation to form chiral β,γ‐cyclohexene. Intriguingly, this olefin serves as a norbornene‐type reagent (presumably assisted by the carboxyl directing effect), relaying two successive Catellani arylation reactions and a C−H arylation reaction to furnish chiral 9,10‐dihydrophenanthrenes along with meta‐selective homocoupling products of iodoarene.