摘要：1 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.

转自：康龙化成

Photoinduced Copper-catalysed Deracemization of Alkyl Halides

Feng Zhong1, Renhe Li1, Binh Khanh Mai2 , Peng Liu2 & Gregory C. Fu1

1 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.

2 Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA.

—Nature, 2025doi:10.1038/s41586-025-08784-8

Recommended by Depei Meng_MC4

KEY WORDS: deracemization, photo chemistry, Cu catalysis, asymmetric synthesis (反应类型), C(sp3)-X (成键类型), alkyl halides (原料),alkyl halides (产物)

ABSTRACT: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. 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.

Deracemization of stereogeniccarbon centres. a, Deracemization is an endergonic process.b, Previous work on photoinduced deracemization. c, This work.

Prof. Gregory C. Fu grouphave developed aphotoinduced copper catalysis method, that enables the deracemization of tertiary (and secondary) alkyl halides, including α,α-dialkyl-α-halocarbonyl compounds, a challenging family of substrates, and related compounds; these products can be further transformed into a wide array of other valuable classes of enantioenriched target molecules through stereoselective reactions with fluorine, carbon, nitrogen and oxygen nucleophiles. The method is straightforward, employing two commercially available reagents that generate the active chiral catalyst in situ.

Gregory C. Fu课题组开发了一种光诱导铜催化方法，该方法能够使叔（和仲）烷基卤化物（包括具挑战性的α，α-二烷基-α-卤代羰基化合物和相关化合物）去消旋化；这些产物可以通过与氟、碳、氮和氧亲核试剂的立体选择性反应进一步转化为各种其他有价值的手性目标分子。该方法简单直接，且使用的手性催化活性物种可由两种市售试剂在原位产生。

来源：新浪财经