Bimetallic Ir/Ru Sequential Catalysis for Stereodivergent Synthesis of Chiral Homoallylic Carbinols Bearing 1,3‐Tertiary/Tertiary Stereocenters

Comprehensive Summary A one‐pot asymmetric cascade allylation/transfer hydrogenation reaction between aryl vinyl carbinols and methyl ketone‐derived silyl enol ethers has been established through bimetallic Ir/Ru sequential catalysis. This protocol enables an efficient approach for the stereoselective construction of a diverse library of chiral homoallylic carbinol derivatives bearing two nonadjacent 1,3‐tertiary/tertiary stereocenters. These structurally important products could be readily obtained in moderate to good yields with excellent stereocontrol (up to 85% yield, >20 : 1 dr, 99% ee), underscoring the robustness and efficiency of the dual catalytic system. Notably, this one‐pot sequential process offers several important advantages, including the use of readily available starting materials, broad substrate scope, and exceptionally high levels of both diastereoselectivity and enantioselectivity. The synthetic utility is further demonstrated by its scalability and operational simplicity; a gram‐scale transformation proceeds smoothly while maintaining both yield and stereoselectivity in one‐pot manner. Moreover, this methodology was well utilized to realize the stereodivergent formal synthesis of the marine natural products calyxolane A and calyxolane B from the same starting materials.