催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (1): 80-85.DOI: 10.1016/S1872-2067(10)60164-7

• 研究论文 • 上一篇    下一篇

带有金刚烷基团的新型手性单齿亚磷酸酯配体的合成及其在不对称1,4-共轭加成反应中的应用

万博1, 邝福儿2, 王来来1, 徐立进3, 赵庆鲁1, 邢爱萍1   

  1. 1中国科学院兰州化学物理研究所，羰基合成与选择氧化国家重点实验室, 甘肃兰州730000; 2香港理工大学应用生物及化学科技学系, 手性药物合成与开发开放实验室, 香港九龙; 3中国人民大学化学系, 北京100049
  • 收稿日期:2010-07-11 修回日期:2010-10-20 出版日期:2011-01-13 发布日期:2014-05-22

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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摘要： 以轴手性的 BINOL/H8-BINOL (BINOL 为联苯酚) 和大位阻的金刚烷酰氯为原料, 合成了系列新型手性单齿亚磷酸酯配体, 并应用于 Cu 催化的二乙基锌对环烯酮的不对称1,4-共轭加成反应中. 结果表明, 配体结构中部分氢化的 2,2′-(1,1′-联萘基) 亚磷酸酯单元和金刚烷基团, 有助于改善反应的对映选择性, 对映选择性最高可达 79%.

关键词: 不对称1,4-共轭加成, 单齿亚磷酸酯配体, 铜盐；环烯酮, 金刚烷；氢八联萘酚单元

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