Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Intermolecular Hydrosilylation of 1,3‐Dienes with Prochiral Silanes

One 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. A new approach for highly regio‐, diastereo‐ and enantioselective intermolecular hydrosilylation of 1,3‐dienes promoted by an easily accessible Co complex to afford a wide range of enantioenriched acyclic silanes was developed. This protocol represents the first intermolecular example of simultaneous construction of a C‐ and a Si‐stereogenic center through metal‐catalyzed hydrosilylation.