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Enantioselective borohydride reduction catalyzed by cobalt complexes: discovery, analysis, and design for a halogen-free system.

  作者 Yamada, Tohru;  
  选自 期刊  Synthesis;  卷期  2008年-10;  页码  1628-1640  
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[摘要]A review. On the basis of a study on the enantioselective version of the oxidn.-redn. hydration catalyzed by bis(1,3-diketonato)cobalt complexes, the highly enantioselective borohydride redn. of carbonyl compds. was developed in the presence of a catalytic amt. of an optically active cobalt(II) complex catalyst. The exptl. and theor. studies on the mechanistic insight of this reaction revealed that the key reactive complexes would be the dichloromethyl-cobalt hydride with a sodium cation, which was generated from chloroform and sodium borohydride. The theor. simulation of various axial groups in active cobalt complex catalysts predicted that the cobalt-carbene complexes could be employed as efficient catalysts. The newly designed complexes generated from cobalt complex and Me diazoacetate made it possible to catalyze the enantioselective borohydride redn. in a completely halogen-free solvent.

 
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