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Alkene difunctionalization

Radical catalysis breaks and makes bonds

Nature Synthesis volume 1, pages 915–916 (2022)Cite this article

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Controllable cleavage and conversion of strong C(sp3)–H bonds remains a challenging task in organic synthesis. Here, a reaction design combining hydrogen atom transfer and copper catalysis is developed which allows enantioselective alkene difunctionalization using aliphatic C–H bond activation.

Now, in Nature Synthesis, Fan et al. report an elegant strategy for alkene difunctionalization that relies on hydrogen atom transfer (HAT) and copper catalysis (Fig. 1b)8. Alkoxyl radicals, derived from the single electron oxidation of a copper(i) catalyst with a benzoperoxoate substrate, serve as key H-atom abstractors leading to aliphatic C–H activation. The concurrent formation of a copper(ii) benzoate complex is responsible for the subsequent radical coupling and enantioselective C–O bond formation. This simplified catalytic system enables the enantioselective difunctionalization of alkenes using hydrocarbons as alkylating reagents, and also provides a general and versatile platform for the stereoselective transformation of hydrocarbons.

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Fig. 1: Enantioselective alkene difunctionalization with compounds containing strong C(sp3)–H bonds.

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  1. Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, China

    Lei Gong

  2. Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, China

    Lei Gong

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  1. Lei Gong
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Correspondence to Lei Gong.

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Gong, L. Radical catalysis breaks and makes bonds. Nat. Synth 1, 915–916 (2022). https://doi.org/10.1038/s44160-022-00174-6

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