Iridium/ruthenium sequential catalysis platform has been established for the stereodivergent construction of chiral homoallylic carbinols. This one-pot tandem protocol leverages readily accessible β-diketones and vinyl ethylene carbonate (VEC) as starting materials, integrating an Ir-catalyzed asymmetric allylation/retro-Claisen cascade process and a subsequent Ru-catalyzed asymmetric transfer hydrogenation (ATH). A diverse array of highly functionalized chiral homoallylic alcohol derivatives containing non-contiguous 1,3-tertiary/tertiary stereocenters could be easily obtained in moderate to good yields with excellent stereoselectivity. Fine manipulation of four distinct chiral Ir/Ru catalyst combinations allows facile access to all four stereoisomers of the target products with excellent stereoselectivity, wherein each stereogenic center is independently and precisely governed by the two distinct chiral catalysts. Furthermore, the practicality of this dual-catalytic protocol is demonstrated by gram-scale synthesis, and the versatile downstream derivatization of the obtained chiral homoallylic alcohols solidifies their utility as robust synthetic building blocks for the construction of complex chiral molecular scaffolds.

Key words: Sequential Catalysis, Chiral Homoallylic Carbinols, Stereodivergent Synthesis, Cascade Reaction, Asymmetric Catalytic Synthesis