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化学学报
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化学学报 ›› 2000, Vol. 58 ›› Issue (9): 1156-1162. 上一篇    下一篇

研究论文

新型P,N配体及基1,4-共轭加成反应

胡信全;陈惠麟;张绪穆   

  1. 中国科学院大连化学物理研究所.大连(116012);The Pennsylvania State University, 152 Davey Laboratory,;University Park
  • 发布日期:2000-09-15

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

Hu Xinquan;Chen Huilin;Zhang Xumu   

  1. Dalian Inst Chem Phys, CAS.Dalian(116012)
  • Published:2000-09-15

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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%。

关键词: 加成反应, 手性拆分, 环己烯酮, 吡啶P, 膦P, 联萘

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(130 of up to 92% e.e. was obtained with 1b as the ligand under the optimum conditions.

Key words: ADDITION REACTION, PYRIDINE P, BINAPHTHYL

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