新型手性膦配体的合成及其在1,4-共轭加成反应中的应用.pdfVIP

2010 Chinese Journal of Catalysis Vol. 31 No. 5 文章编号: 0253-9837(2010)05-0514-04 国际版 DOI : 10.1016/S1872-2067(09)60063-2 研究快讯: 514~517 新型手性膦配体的合成及其在 1,4-共轭加成反应中的应用 1,2 1,2 1 万 博 , 赵庆鲁 , 王来来 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 中国科学院研究生院, 北京 100049 摘要：以联萘酚和大位阻的金刚烷酰氯为原料, 经两步合成了系列新型手性单齿亚磷酸酯配体, 并应用于铜催化的二乙基锌对 环烯酮的不对称 1,4-共轭加成反应. 结果表明, 产物收率和对映选择性最高分别为 95% 和 61%. 配体 (S)-(2-(adamantane- 1-carboxylic acid)-1,1’-binapthalen-2’-yl)-((S)-1,1’-binaphthalen-2,2’-yl)phosphite [(S,S)-3a] 的两个 (S)-联萘酚构型是匹配的组合, 产物的绝对构型主要由配体中 2,2’-二氧膦-1,1’-联萘酚的构型控制. 关键词：不对称 1,4-共轭加成; 单齿亚磷酸酯; 2-环己烯酮; 二乙基锌; 对应选择性 中图分类号：O643 文献标识码：A Synthesis of Chiral Bulky Monophosphite Ligands and Their Application in Cu-Catalyzed Asymmetric Conjugate Addition of Diethylzinc to Cyclic Enones WAN Bo1,2, ZHAO Qinglu1,2, WANG Lailai1,* 1State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China 2 Graduate University of Chinese Academy of Sciences, Beijing 100049, China Abstract: A series of new bulky monophosphite ligands were synthesized from axially chiral BINOL and highly sterically hindered ada- mantanecarbonyl chloride. These ligands were applied to the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclic enones and were found to have m