Wang Kun, Niu Saisai, Tang Weijun, Xue Dong, Xiao Jianliang, Li Hongfeng, Wang Chao
Huzhou Key Laboratory of Green Energy Materials and Battery Cascade Utilization, School of Intelligent Manufacturing, Huzhou College, Huzhou, 313000, China.
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China.
Chem Commun (Camb). 2024 Apr 16;60(32):4338-4341. doi: 10.1039/d4cc00356j.
Ru-catalyzed asymmetric hydrogenation of α-substituted α,β-unsaturated ketones has been developed for the enantioselective synthesis of chiral α-substituted secondary alcohols with high diastereo- and enantioselectivities (up to >99 : 1 dr, 98% ee). Mechanistic experiments suggest that the reaction proceeds a Ru-catalyzed asymmetric hydrogenation of the CO bond in concert with a base-promoted allylic alcohol isomerization, and the final stereoselectivities were controlled by a DKR process during the asymmetric hydrogenation of the ketone intermediate.
钌催化的α-取代α,β-不饱和酮的不对称氢化反应已被用于对映选择性合成具有高非对映和对映选择性（高达>99:1 dr，98% ee）的手性α-取代仲醇。机理实验表明，该反应通过钌催化的CO键不对称氢化与碱促进的烯丙醇异构化协同进行，最终的立体选择性在酮中间体的不对称氢化过程中由动态动力学拆分（DKR）过程控制。
