Regio-controllable Cobalt-Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes.

Regiodivergent addition reactions provide straightforward and atom-economic approaches to access different regioisomers. However, the regio-chemistry control to access all the possible results is still challenging especially for the reaction involving multiple addition steps. Herein, we reported regio-controllable cobalt-catalyzed sequential hydrosilylation/hydroboration of arylacetylenes, delivering all the possible regio-outcomes with high regioselectivities (up to >20/1 rr for all the cases). Each regioisomer of value-added silylboronates could be efficiently and regioselectively obtained from the same materials. The adjustment of the ligands of cobalt catalysts combined with dual catalysis relay strategy is the key to achieve regio-chemistry control. This regio-controllable research might inspire the exploration of the diversity-oriented synthesis that involves multiple additions and provide full sets of regioisomers of other synthetic useful molecules.