新型P,N配体及基1,4-共轭加成反应

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%。

synthesis of novel P,N ligands and their application in enantioselective 1,4-conjugate addition

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.