Chinese Journal of Catalysis

Chinese Journal of Catalysis ›› 2011, Vol. 32 ›› Issue (1): 80-85.DOI: 10.1016/S1872-2067(10)60164-7

• Research papers • Previous Articles     Next Articles

New Chiral Monophosphite Ligands Containing BINOL and/or H8-BINOL Bearing Adamantyl Substituents: Effect of Ligand Scaffold on the Enantioselective 1,4-Conjugate Addition of Diethylzinc to Cyclic Enones

WAN Bo1, KWONG Fuk Yee2,#, WANG Lailai1,*, XU Lijin3, ZHAO Qinglu1, XING Aiping1   

  1. 1State Key Laboratory for Oxo Synthesis & Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China; 2Open Laboratory of Chirotechnology of the Institute of Molecular Technology for Drug Discovery and Synthesis, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Kowloon, Hong Kong, China; 3Department of Chemistry, Renmin University of China, Beijing 100049, China
  • Received:2010-07-11 Revised:2010-10-20 Online:2011-01-13 Published:2014-05-22

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Abstract: A series of new bulky monophosphite ligands were synthesized from axially chiral BINOL/H8-BINOL (BINOL: 1-(2-hydroxynaphthalen-1-yl)naphthalen-2-ol) and highly sterically hindered adamantylcarbonyl chloride. The effectiveness of these ligands was evaluated by the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclic enones with enantioselectivities of up to 79% ee. The results showed that a ligand structure comprising a partially hydrogenated 2,2′-(1,1′-binaphthyl)phosphite scaffold and an adamantyl moiety was effective in improving the enantioselectivity.

Key words: enantioselective 1,4-conjugate addition, phosphite ligand, copper salt, cyclic enone, adamantyl, H8-binaphtyl