Metal hydride selection enables cross- and branched-selective hydroalkenylation

ABSTRACT This study describes a strategy for selecting metal hydrides to achieve efficient and highly selective cross- and branched hydroalkenylation. By combining 2,6-lutidinium tetrafluoroborate with manganese as a mild reductant, cobalt hydride is selectively generated under nickel catalysis, leading to cross-selective alkene–alkene coupling and furnishing valuable branched products with exceptional selectivity.