Nickel-catalyzed hydro- and deuteroacylation of acrylates using water as the hydrogen source

Acylation of activated alkenes provides useful and quick access to synthetically useful 1,4-difunctionalized compounds. In this work, an operationally simple mechanochemical protocol for the hydroacylation of acrylates and related activated alkenes is reported using thioesters as acyl donors and water as the hydrogen source. This approach selectively furnished linear coupling products, complementing previous nickel-catalyzed methodologies that predominantly yielded branched 1,3-adducts. Substitution of water with D₂O enables straightforward synthesis of deuterium-labeled products with high levels of selective isotopic incorporation. Detailed mechanistic investigations, including primary and secondary KIE studies, Hammett analysis, DFT computations and NMR spectroscopy, support a pathway involving migratory insertion at the nickel center, while providing no evidence for the involvement of radical intermediates.