Asymmetric Substitution by Alkynyl Copper Driven Dearomatization and Rearomatization

• DOI: 10.1002/anie.202314517
• Publication Date: 2023-10-16T15:05:46Z
• Authors: Yu‐Ze Sun; Zi‐Yang Ren; Yuan‐Xiang Yang; Yang Liu; Guo‐Qiang Lin; Zhi‐Tao He
• Keywords: Heteroatom; Substitution (logic)

Abstract Catalytic asymmetric transformations by dearomatization have developed into a widely applicable synthetic strategy, but heavily relied on the use of arenes bearing heteroatom. In this case, is facilitated involvement p ‐orbital electron Different from conventional substrate‐dependent model, here we demonstrate that activation d transition‐metal center can serve as driving force for dearomatization, and applied to development novel alkynyl copper remote substitution reaction. A newly modified PyBox chiral ligand enables construction valuable diarylmethyl triarylmethyl skeletons in high enantioselectivities. An unexpected tandem process involving sequential substitution/cyclization/1,5‐H shift leads formation enantioenriched C−N axis. gram‐scale reaction various downstream highlight robustness method potential products. Preliminary mechanistic studies reveal mononuclear Cu‐catalyzed process.