胡向平.苯乙胺衍生的手性膦-亚磷酰胺酯配体在Rh-催化a-烯醇酯膦酸酯的不对称氢化反应中的应用[J].分子催化,2012,(6):487-492
苯乙胺衍生的手性膦-亚磷酰胺酯配体在Rh-催化a-烯醇酯膦酸酯的不对称氢化反应中的应用
Rh-Catalyzed Asymmetric Hydrogenation of a-Enol Ester Phosphonates with 1-Phenylethylamine-Derived Phosphine-Phosphoramidite Ligands
投稿时间:2012-11-08  修订日期:2012-12-01
DOI:
中文关键词:  不对称催化    膦-亚磷酰胺酯配体  a-烯醇酯膦酸酯  氢化
英文关键词:asymmetric catalysis  rhodium  phosphine-phosphoramidite ligand  a-enol ester phosphonate  hydrogenation
基金项目:The National Natural Science Foundation of China (General Program, Key Program, Major Research Plan)
作者单位E-mail
胡向平* 中国科学院大连化学物理研究所 xiangping@dicp.ac.cn 
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中文摘要:
      将苯乙胺衍生的手性膦-亚磷酰胺酯配体应用在Rh-催化a-烯醇酯膦酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性最高>99% ee.
英文摘要:
      A series of phosphine-phosphoramidite ligands derived from commercially available, inexpensive chiral 1-phenylethylamine were employed in the Rh-catalyzed asymmetric hydrogenation of various a-enol ester phosphonates. The results indicated that the ligand (Sc,Sa)-2b bearing a Me-group on amino moiety exhibited similar enantioselectivity but superior catalytic activity to (Rc,Ra)-THNAPhos. Excellent enantioselectivities (up to >99% ee) and high catalytic activity (S/C up to 5000) have been achieved in the hydrogenation of various b-alkyl and b-aryl substituted substrates, demonstrating the high potential of this phosphine-phosphoramidite ligand in the preparation of optically active a-hydroxyphosphonates
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