Asymmetric Substitution by Alkynyl Copper Driven Dearomatization and Rearomatization

Author:

Sun Yu‐Ze12,Ren Zi‐Yang13,Yang Yuan‐Xiang1,Liu Yang1,Lin Guo‐Qiang123,He Zhi‐Tao14ORCID

Affiliation:

1. CAS Key Laboratory of Synthetic Chemistry of Natural Substances Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Shanghai 200032 China

2. Department of Chemistry Shanghai Normal University Shanghai 200234 China

3. School of Physical Science and Technology ShanghaiTech University Shanghai 201210 China

4. School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou 310024 China

Abstract

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

Funder

National Natural Science Foundation of China

Natural Science Foundation of Ningbo Municipality

Science and Technology Commission of Shanghai Municipality

Publisher

Wiley

Subject

General Medicine

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