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Electrochemical NiH‐Catalyzed C(sp<sup>3</sup>)−C(sp<sup>3</sup>) Coupling of Alkyl Halides and Alkyl Alkenes

Pengfei Li, Guangsheng Kou, Tian Feng, Minyan Wang, Youai Qiu

2023Angewandte Chemie International Edition47 citationsDOIOpen Access PDF

Abstract

Abstract Herein, an electrochemically driven NiH‐catalyzed reductive coupling of alkyl halides and alkyl alkenes for the construction of C sp 3 −C sp 3 bonds is firstly reported. Notably, alkyl halides serve dual function as coupling substrates and as hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature of this reaction is realized by introducing an intramolecular coordinating group to the substrate, where the product can be easily adjusted to give the desired branched products. The method proceeds under mild conditions, exhibits a broad substrate scope, and affords moderate to excellent yields with over 70 examples, including late‐stage modification of natural products and drug derivatives. Mechanistic insights offer evidence for an electrochemically driven coupling process. The sp 3 ‐carbon‐halogen bonds can be activated through single electron transfer (SET) by the nickel catalyst in its low valence state, generated by cathodic reduction, and the generation of NiH species from alkyl halides is pivotal to this transformation.

Topics & Concepts

AlkylHalideChemistryCatalysisElectrochemistryIntramolecular forceHalogenPhotochemistryMedicinal chemistryOrganic chemistryPhysical chemistryElectrodeCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsCO2 Reduction Techniques and Catalysts
Electrochemical NiH‐Catalyzed C(sp<sup>3</sup>)−C(sp<sup>3</sup>) Coupling of Alkyl Halides and Alkyl Alkenes | Litcius