2019/07/06 by Hua Wu, Qian Wang, Jieping Zhu · 1 citation
Chemistry · #Asymmetric Synthesis and Catalysis #Asymmetric Hydrogenation and Catalysis #Synthetic Organic Chemistry Methods
paper · doi:10.1021/jacs.9b04551
openalex publication_date 2019/07/06 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
The development of enantioselective pinacol rearrangement is extremely challenging due to the likelihood involvement of the carbenium intermediate that renders the stereochemical communication between catalyst and substrate difficult to achieve. Herein, we report chiral N -triflyl phosphoramide-catalyzed enantioselective pinacol rearrangement of 1,2-tertiary diols and mechanistically related Meinwald rearrangement of tetrasubstituted epoxides for the synthesis of enantioenriched 2-alkynyl-2-arylcyclohexanones and 2,2-diarylcyclohexanones, respectively. Total synthesis of (+)-mesembrane featuring the catalytic enantioselective pinacol rearrangement as a key strategic step is also documented.