铜(Ⅰ)配合物的不对称催化1,4-共轭加成反应  

Enantioselective 1,4-Conjugate Addition Catalyzed by Cu(Ⅰ) Complexes

作　　者：胡信全[1] 陈惠麟[1] 张绪穆[2] 

机构地区：[1]中国科学院大连化学物理研究所 [2]The Pennsylvania State University,152 Davey Laboratory,University Park,PA 16802,USA

出　　处：《化学学报》2000年第9期1163-1167,共5页Acta Chimica Sinica

摘　　要：以两个新型手性配体S-(+)-2-(2-吡啶酚胺基)-2＇-(二苯基膦基)-1,1＇-联萘(1a)和S-(+)-2-(6-甲基-2-吡啶酚胺基)-2＇-(二苯基膦基)-1,1＇-联萘(1b)的铜配合物催化的二乙基锌对开链烯酮的1,4-共轭加成反应的研究.以1a为标准配体,查耳酮为代表性废物,考察了溶剂、催化剂前体等因素对反应的影响.在优化条件下,系统研究了以[Cu(OTf)](C_6H_6)_(1/2)/1b为催化剂,甲苯-二氯乙烷为溶剂时进行了二乙基锌对七个开链烯酮的1,4-共轭加成反应,取得了突破性进展,获得最高达98％e.e.值的加成产物.The Cu - catalyzed enantioselective 1,4- conjugate addition has been achieved with S - ( + ) -2 - (2 - pyridinylcarboxamido) - 2' - (diphenylphosphino) -1,1'- binaphthyl (1a) and S-( + )-2-(6 -methyl - 2 - pyridinylcarboxamido) - 2' - (diphenylphosphino) - 1,1' - binaphthyl (1b) ligands. The reaction conditions such as the solvents and catalyst precursors were investigated using 1a as the ligand and chalcone (2a) as the typical substrate. Under the optimized conditions, the Cu( I ) -1b complex catalyzed enan tioselective 1,4- conjugate additions of diethylzinc to acyclic enones (2) were systematically studied. The unprecedented high enantioselectivity (up to 98 % ) has been achieved.

关 键 词：不对称催化 1 4-共轭加成 P N-配体 铜配合物 

分 类 号：O643.3[理学—物理化学]