手性磷酸催化的有机催化不对称反应  

Organocatalytic Asymmetric Reaction Catalyzed by Chiral Phosphoric Acids

作　　者：高勇军[1] 杨丽华[1] 宋双居[1] 马晶军[1] 唐然肖[1] 边瑞环[1] 刘海燕[1] 吴秋华[1] 王春[1] 

机构地区：[1]河北农业大学理学院河北省生物无机化学重点实验室,保定071001

出　　处：《有机化学》2008年第1期8-16,共9页Chinese Journal of Organic Chemistry

基　　金：河北农业大学非生命学科和新兴学科科研发展基金

摘　　要：手性磷酸是近年来发展起来的一类新型高效、高对映选择性的Br(?)nsted酸类有机催化剂,已成功应用于催化不对称Mannich反应、还原胺化反应、Pictet-Spengler反应、aza-Diels-Alder反应和aza-Ene反应等许多重要的有机合成反应.手性磷酸催化剂分子内同时含有Lewis碱性位点和Br(?)nsted酸性位点,可同时活化亲电与亲核底物.作为一种新型双功能有机催化剂,手性磷酸具有较高的催化活性和对映选择性,催化剂最低用量可达0.05 mol%.对各类手性磷酸催化剂在有机催化不对称合成反应中的应用研究进展,以及不对称诱导反应的机理、手性磷酸的分子结构及反应条件对其催化活性和不对称诱导活性的影响进行了评述.Chiral phosphoric acids are highly efficient and enantioselective of BrФnsted acid organocatalysts discovered very recently. High yields and excellent enantioselectivity were achieved in asymmetric organic reactions involving imines, such as asymmetric Mannich, reductive amination, Pictet-Spengler, aza-Diels-Alder, aza-ene reactions and so on. The presence of the Lewis basic phosphoryl moiety in proximity to the BrФnsted acidic proton in chiral phosphoric acids potentially allows for bifunctional catalysis, that is, simultaneous activation of both electrophilic and necleophilic reaction components. The catalyst loading could be lowered to 0.5 mol%. The applications of chiral phosphoric acids in asymmetric organocatalytic reactions are reviewed. The reaction mechanism, catalytic activity and the asymmetric induction influenced by the structure of chiral phosphoric acids and the reaction conditions are also discussed.

关 键 词：不对称有机催化 对映选择性 手性磷酸 综述 

分 类 号：O643.32[理学—物理化学]