Photoinduced copper-catalysed deracemization of alkyl halides
成果类型：
Article
署名作者：
Zhong, Feng; Li, Renhe; Mai, Binh Khanh; Liu, Peng; Fu, Gregory C.
署名单位：
California Institute of Technology; Pennsylvania Commonwealth System of Higher Education (PCSHE); University of Pittsburgh
刊物名称：
Nature
ISSN/ISSBN：
0028-1897
DOI：
10.1038/s41586-025-08784-8
发表日期：
2025-04-03
关键词：
摘要：
Deracemization is an emerging strategy for generating enantioenriched compounds wherein the two enantiomers of a readily available racemic starting material are transformed into a single enantiomer, typically through the action of a light-induced catalyst(1,2). Excellent proof of principle for this potentially powerful approach to asymmetric catalysis has been described(3, 4, 5, 6, 7-8); nevertheless, substantial challenges have not yet been addressed, including the exploitation of carbon-heteroatom (rather than only carbon-hydrogen and carbon-carbon) bond cleavage to achieve deracemization, as well as the development of processes that provide broad classes of useful enantioenriched compounds and tetrasubstituted stereocentres. Here we describe a straightforward method that addresses these challenges, using a chiral copper catalyst, generated in situ from commercially available components, to achieve the photoinduced deracemization of tertiary (and secondary) alkyl halides through carbon-halogen bond cleavage. Mechanistic studies (including the independent synthesis of postulated intermediates, photophysical, spectroscopic and reactivity studies, and density functional theory calculations) provide support for the key steps and intermediates in our proposed catalytic cycle, as well as insight into the origin of enantioselectivity.