Copper(II)-Catalyzed ortho-Selective C-H Allylation of Tertiary Anilines with Unprotected Allyl Alcohols

Regioselective functionalization of arene C-H bonds stands as a forefront research area in modern synthetic organic chemistry. Among such transformations, C-H allylation represents a fundamentally important strategy for forging C-C bonds, with broad utility in the assembly of structurally diverse organic molecules. Herein, we disclose an unprecedented copper(II)-catalyzed protocol for the ortho-selective C-H allylation of tertiary anilines using unprotected allyl alcohols as alkylating agents. Remarkably, this reaction proceeds without external ligands, additives, or stoichiometric oxidants, thus minimizing synthetic waste and streamlining operational complexity. This reaction tolerated various substituted tertiary anilines and allyl alcohols, affording the corresponding ortho allylation products in moderate to good yields. The reactions were effectively scaled up, affording the corresponding allylation products in good yields. Preliminary mechanistic studies suggest a catalytic cycle involving a π-allylcopper intermediate. This method provides a cost-effective, atom-economical alternative to precious metal-catalyzed allylation reactions.