Titanium-Catalyzed Reductive Umpolung Reactions with A Metal-Free Terminal Reducing Agent
Chemistry(2015)
摘要
A new method for titanium-catalyzed reductive umpolung reactions is reported that overcomes the traditional requirement for a stoichiometric metallic reductant. With N, N'-disilylated tetramethyldihydropyrazine as a potent organic reducing agent, reductive carbonyl-nitrile, enone-acrylonitrile and pinacol coupling reactions can be achieved in good yields and stereoselectivities. [Cp2TiI2] is a superior catalyst to [Cp2TiCl2], which is rationalized by a faster generation of the active catalyst [Cp2TiI]. A mechanism is proposed that is in agreement with the experimental results.
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关键词
homogeneous catalysis,radicals,reductive coupling,titanium,umpolung
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