新型P,N配体及其1,4-共轭加成反应  

Synthesis of Novel P,N Ligands and Their Application in Enantioselective 1,4-Conjugate Addition

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1156-1162,共7页Acta Chimica Sinica

摘　　要：以2-萘酚为起始原料,经过氧化偶联,消旋体的拆分得到手性骨架2-氨基-2＇-羟基-1,1＇-联萘(NOBIN).并以S-NOBIN为原料,经过六步反应合成了两个新型配体S-(+)-2-(2-吡啶酰胺基)-2＇-二苯基膦基-1,1＇-联萘(1a)和S-(+)-2-(6-甲基-2-吡啶酰胺基)-2＇-二苯基膦基-1,1＇-联萘(1b).并进行了铜配合物催化的二乙基锌对2-环己烯酮的1,4-共轭加成反应的研究.反应产物3-乙基环己酮(13)的e.e.值高达92％.Chiral 2 - amino - 2' - hydroxy - 1,1' - binaphthyl (NOBIN) was obtained by resolution of racemic NOBIN, which was prepared by catalytic cross - coupling of 2 - naphthol and 2 - amino -naphthylene. Two structurally novel chiral P, N ligands, S-( + )-2-(2- pyridinyl - carboxamido) - 2' -diphenylphosphino -1,1'- binaphthyl(1a)and S -( + )-2-(6- methyl - 2 - pyridinylcarboxamido) -2' - diphenyl-phosphino -1,1'- binaphthyl (1b) , were synthesized in six steps from the chiral framework of S - NOBIN. The enantioselective 1,4- conjugate addition of diethylzinc to 2 - cyclohexen - 1 - one catalyzed by Cu( I )/1 complexes was performed. 3 - ethylcyclohexanone(13) of up to 92 % e. e. was obtained with 1b as the ligand under the optimum conditions.

关 键 词：P N-配体 1 4-共轭加成 2-环已烯酮 二乙基锌 

分 类 号：O643.3[理学—物理化学]