Asymmetric Transfer Hydrogenation of Naphthol and Phenol Derivatives with Cooperative Heterogeneous and Homogeneous Catalysis  

作　　者：Xiaolin Li Wei Hao Niannian Yi Yan-Mei He Qing-Hua Fan 

机构地区：[1]Beijing National Laboratory for Molecular Sciences,CAS Key Laboratory of Molecular Recognition and Function,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190 [2]University of Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2023年第10期2277-2289,共13页中国化学会会刊(英文)

基　　金：the National Key R&D Program of China(grant no.2021YFA1500200);the National Natural Science Foundation of China(grant nos.92256303 and 92056108)for financial support.

摘　　要：Asymmetric hydrogenation of all-carbon aromatics is still a long-standing challenge in the area of asymmetric catalysis.To date,asymmetric(transfer)hydrogenation of naphthols and phenols remains unexplored.Here,we describe a new strategy for such asymmetric transformation via a bimetallic cooperative heterogeneous and homogeneous catalysis.By using HCOONa as the hydrogen source,various naphthols and phenols were partially hydrogenated in HFIP catalyzed by commercial Pd/C catalyst to give ketone intermediates.Further adding the second chiral Ru-tethered-TsDPEN catalyst and MeOH realized the asymmetric reduction of the resulting ketones in a one-pot manner,furnishing chiral alcohols with good to excellent enantioselectivity(up to 99%ee).The use of HFIP is crucial for suppressing ketone over-reduction via heterogeneous catalysis.More importantly,tandem asymmetric transfer hydrogenation of naphthols was also achieved by tuning the volume ratio of mixed HFIP/MeOH solvent,affording chiral 1,2,3,4-tetrahyronaphthols with excellent enantioselectivity but relatively low yield and limited substrate scope.

关 键 词：enantioselective hydrogenation arenols bimetallic catalysis heterogeneous catalysis homogeneous catalysis 

分 类 号：O621.251[理学—有机化学]