Diastereodivergent and Enantioselective Synthesis of Homoallylic Alcohols via Nickel-Catalyzed Borylative Coupling of 1,3-Dienes with Aldehydes
Jin-Tao Ma, Tianze Zhang, Bo-Ying Yao, Li‐Jun Xiao, Qi‐Lin Zhou
Abstract
We present the first enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes, providing an efficient route to highly valuable homoallylic alcohols in a single step. The reaction involves the 1,4-carboboration of dienes, leading to the formation of C–C and C–B bonds accompanied by the construction of two continuous stereogenic centers. Enabled by a chiral spiro phosphine-oxazoline nickel complex, this transformation yields products with exceptional diastereoselectivity, E -selectivity, and enantioselectivity. The diastereoselectivity of the reaction can be controlled by employing either ( Z )-1,3-dienes or ( E )-1,3-dienes.
Topics & Concepts
ChemistryEnantioselective synthesisStereocenterNickelCatalysisOxazolinePhosphineSelectivityStereoselectivityCombinatorial chemistryOrganic chemistryMedicinal chemistryStereochemistryOrganoboron and organosilicon chemistryAsymmetric Hydrogenation and CatalysisAdvanced Synthetic Organic Chemistry