Directed Markovnikov hydroarylation and hydroalkenylation of alkenes under nickel catalysis

We report a full account of our research on nickel-catalyzed Markovnikov-selective hydroarylation and hydroalkenylation of non-conjugated alkenes, which has yielded a toolkit of methods that proceed under mild conditions with alkenyl sulfonamide, ketone, and amide substrates. Regioselectivity is controlled through catalyst coordination to the native Lewis basic functional groups contained within these substrates. To maximize product yield, reaction conditions were fine-tuned for each substrate class, reflecting the different coordination properties of the directing functionality. Detailed kinetic and computational studies shed light on the mechanism of this family of transformations, pointing to transmetalation as the turnover-limiting step.

Automated summary

Research on nickel-catalyzed Markovnikov-selective hydroarylation and hydroalkenylation of non-conjugated alkenes has developed a toolkit of methods that can react with various substrates under mild conditions, with regioselectivity controlled through catalyst coordination with functional groups within the substrates. Reaction conditions were adjusted for each substrate class to maximize product yield, and detailed studies shed light on the mechanism of these transformations, highlighting transmetalation as the turnover-limiting step.