Highly Efficient and Markovnikov-Selective Cobalt Catalysis for the Construction of α‑Alkenylboronates

α-Alkenylboronates are appealing building blocks in organic synthesis, as well as promising monomers in polymerization. Herein, we report a cobalt-catalyzed highly efficient Markovnikov-selective hydroboration of terminal alkynes enabled by a recently developed ligand to access α-alkenylboronates. This operationally simple protocol not only exhibits good functional group tolerance but also demonstrates compatibility with primary, secondary, and sterically hindered tertiary aliphatic alkynes. Fourteen examples of gram-scale reactions have been shown even with only 0.05 mol % catalyst loading to deliver the corresponding products that could be easily purified through distillation or recrystallization. Based on the control experiments, the anti-interference ligand could inhibit the coordination of boranes, improving the compatibility and regioselectivity of this transformation.