Catalysis

Acetate Facilitated Nickel Catalyzed Coupling of Aryl Chlorides and Alkyl Thiols

Authors

Abstract

We report a mild, fast and convenient catalytic system for the coupling of aryl chlorides with primary, secondary, as well as previously challenging tertiary alkyl thiols using an air-stable nickel(II) precatayst in combination with the low-cost base potassium acetate at room temperature. This new catalytic system tolerates a variety of functional groups and enables the generation of thioethers for a wide range of substrates, including pharmaceutical compounds in excellent yields. Chemoselec-tive functionalization of disubstituted substrates was demonstrated. Kinetic and NMR-studies, as well as DFT computations support a Ni(0)/Ni(II) catalytic cycle and identify the oxidative addition product as the resting state. Acetate coordination and subsequent acetate facilitated formation of a thiolate complex via internal deprotonation play a key role in the catalytic cycle.

Content

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Supplementary material

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Supporting Information
Experimental and computational data