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化学学报
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化学学报 ›› 2000, Vol. 58 ›› Issue (9): 1163-1167. 上一篇    下一篇

研究论文

铜(Ⅰ)配合物的不对称催化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

Enantioselective 1,4-conjugate addition catalyzed by Cu(Ⅰ) complexes

Hu Xinquan;Chen Huilin;Zhang Xumu   

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

PDF

474

被引次数

2

以两个新型手性配体S-(+)-2-(2-吡啶酰胺基)-2'-(二苯基膦基)-1,1'-联苯(1a)和S-(+)-2-(6-甲基-2-吡啶酰胺基)-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，查耳酮为代表性底物，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。

关键词: 铜络合物, 催化反应, 加成反应, 吡啶P, 膦P, 联萘P, 烯酮, 锌化合物

The Cu-catalyzed enantioselective 1,4-conjugate addition has been achieved with 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) 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.

Key words: COPPER COMPLEX, CATALYTIC REACTION, ADDITION REACTION, BINAPHTHYL P, KETENE, ZINC COMPOUNDS

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