Copper‐Catalyzed Radical Enantioconvergent C─O Bond Formation for Asymmetric Cross‐Coupling of Allylamines and CO ₂

Abstract

Abstract Upgrading abundant carbon dioxide (CO 2 ) into high‐value organic molecules has garnered broad research interest for decades. Within this domain, catalytic asymmetric synthesis employing CO 2 holds great synthetic importance. Although remarkable advances have been made in asymmetric C─C bond formation using CO 2 as a C1 synthon in recent years, the development of incorporation of CO 2 as an oxygen source for asymmetric C─O bond construction remains elusive, presumably due to the formidable challenge of simultaneously addressing enantioselectivity control and reaction efficiency. Here, we demonstrate the first copper‐catalyzed asymmetric C─O bond cross‐coupling of allylamines and CO 2 in a radical strategy. The key innovation resides in the rational and strategic conversion of C 2 ‐symmetric oxazoline ligands to their C 1 ‐symmetric counterparts, which induces additional C─N axial chirality after coordination with copper. The resultant enantioenriched fluoroalkylated 2‐oxazolidones can be further transformed into diverse functional compounds, including novel chiral amino alcohols for oxazoline ligand design and a potent bioactive insecticide analogue. Detailed mechanistic investigations elucidate a radical‐mediated pathway and establish the critical role of C 1 ‐symmetric ligands in achieving efficient stereochemical control.