轉(zhuǎn)自：康龍化成
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, 2025,doi:10.1038/s41586-025-08784-8
Recommended by Depei Meng_MC4
KEY WORDS: deracemization, photo chemistry, Cu catalysis, asymmetric synthesis (反應(yīng)類型), C(sp3)-X (成鍵類型), alkyl halides (原料),alkyl halides (產(chǎn)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.
Photoinduced copper-catalysedderacemization ofα,α-dialkyl-α-haloamides
Photoinduced copper-catalysedderacemization of other classes of electrophiles and synthetic utility.
Plausible Mechanism
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課題組開發(fā)了一種光誘導(dǎo)銅催化方法，該方法能夠使叔（和仲）烷基鹵化物（包括具挑戰(zhàn)性的α，α-二烷基-α-鹵代羰基化合物和相關(guān)化合物）去消旋化；這些產(chǎn)物可以通過(guò)與氟、碳、氮和氧親核試劑的立體選擇性反應(yīng)進(jìn)一步轉(zhuǎn)化為各種其他有價(jià)值的手性目標(biāo)分子。該方法簡(jiǎn)單直接，且使用的手性催化活性物種可由兩種市售試劑在原位產(chǎn)生。
（轉(zhuǎn)自：康龍化成）
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