Enantioselective Synthesis of Atropisomeric 1,3‐Dienes via Platinum‐Catalyzed Hydrosilylation of 1,3‐Enynes

The enantioselective synthesis of novel atropisomeric architectures represents a key driving force in the advancement of functional materials, drug discovery, and asymmetric catalysis. While great progress has been made in the enantioselective synthesis of biaryl atropisomers, the catalytic enantioselective synthesis of atropisomeric acyclic 1,3‐dienes is still elusive due to the inherently low rotational barrier of the C‐C bonds. Herein, we report a platinum‐catalyzed enantioselective hydrosilylation of enynes. Using a monophosphine ligand L1 , the atropisomeric 1,3‐dienes are constructed in good yield with enantioselectivity and excellent regio‐ and E ‐selectivity. Density functional theory (DFT) calculations are conducted to elucidate the origin of the regio‐ and enantioselectivity. Crucially, the basic additive such as KOH and K 3 PO 4 works as a proton shuttle to promote the reaction.