Self-Assembly of Heterobimetallic Complexes and Reactive Nucleophiles: A General Strategy for the Activation of Asymmetric Reactions Promoted by Heterobimetallic Catalysts
作者： Takayoshi Arai , Yoichi M. A. Yamada , Noriyoshi Yamamoto , Hiroaki Sasai , Masakatsu Shibasaki
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摘要: Heterobimetallic asymmetric catalysts, such as the lanthanum–lithium–binaphthol complex (La Li–BINOL), aluminum–lithium–binaphthol (AlLi–BINOL), and a newly prepared gallium–sodium–binaphthol (Ga Na–BINOL), have been self-assembled with reactive nucleophiles, lithium nitronates sodium malonates, to generate more efficient catalysts than parent heterobimetallic catalysts. For example, by combined use of La Li–BINOL (1 mol%; contains one H2O molecule) BuLi (0.9 mol%) catalyst system, nitroaldol reactions are greatly accelerated in all cases without decrease optical purity products. Kinetic analyses also carried out on Ga Na–BINOL-catalyzed Michael reaction dibenzyl malonate cyclohexenone, or NaOtBu. The calculated rate constants show that Na–BINOL NaOtBu gives rates about 50 times faster alone. This activation method should be useful for other catalyzed complexes.
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