Abstract

AbstractOne of the most straightforward approaches to access chiral silanes is catalytic enantioselective hydrosilylation. Although significant advances have been achieved in enantioselective construction of either a carbon‐stereogenic center or a silicon‐stereogenic center through enantioselective hydrosilylation, simultaneous establishment of a carbon‐ and a silicon‐stereogenic center in an acyclic molecule through a single intermolecular hydrosilylation remained undeveloped. Herein, an unprecedented cobalt‐catalyzed regio‐, diastereo‐ and enantioselective hydrosilylation of 1,3‐dienes is presented, enabling construction of a carbon‐ and a silicon‐stereogenic center in a single intermolecular transformation. A wide range of chiral silanes bearing a carbon‐ and a silicon‐stereogenic center were generated in high efficiency and stereoselectivity. Functionalization of the enantioenriched silanes delivered a variety of valuable chiral building blocks that are otherwise difficult to access.

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