A Catalytic asymmetric Strecker-Type Reaction Promoted by Lewis Acid-Lewis Base Bifunctional Catalvst
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概要
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A general asymmetric Strecker-type reaction is reported, catalyzed by the Lewis acid-Lewis base bifunctional catalyst 1. The reaction of trimetylsilyl cyanide (TMSCN) with various fluorenyl imines, including n-aldimines and α, β-unsaturated imines, proceeds with good to excellent enantioselectivities in the presence of a catalytic amount of phenol as additive (20 mol%)(catalytic system 1). The products were successfully converted to the corresponding amino acid derivatives in high yields without loss of enantiomeric purity. Furthermore, hydrogenation or dihydroxylation of the products from α, β-unsaturated imines afforded saturated or functionalized aminonitriles also without loss of enantiomeric putiry. The absolute configuration of the products and a control experiment using catalyst 2 supported the proposed dual activation of the imine and TMSCN by the Lewis acid (Al) and the Lewis base moiety (phosphine oxide) of 1. From the mechanistic studies including kinetic and NMR experiments of the catalytic species, the role of PhOH seems to be a proton source to protonate the anionic nitrogen of the intermediate. Specifically, we have found that TMSCN is more reactive than HCN in this catalytic system, probably due to the activation ability of the phosphine oxide moiety of 1 toward TMSCN. This fact prompted us to develop the novel catalytic system 2,consisting of 1 (9 mol%), TMSCN (20 mol%) and HCN(1.2 mol eq). This new system afforded comparable results with obtained by system 1 (1 (9 mol%)-TMSCN(2 mol eq)-PhOH (20 mol%)).
- 公益社団法人日本薬学会の論文
- 2000-10-01
著者
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柴崎 正勝
東大 大学院
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金井 みち子
Finnigan Mat Instruments Inc.
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金井 求
Graduate School Of Pharmaceutical Sciences The University Of Tokyo
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Kanai Motomu
Graduate School Of Pharmaceutical Science The University Of Tokyo
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Usuda Hiroyuki
Graduate School Of Pharmaceutical Sciences The University Of Tokyo
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Usuda Hiroyuki
Graduate School Of Life And Environmental Sciences University Of Tsukuba
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Shibasaki Masakatsu
Graduate School Of Pharmaceutical Science The University Of Tokyo
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TAKAMURA Masahiro
Graduate School of Pharmaceutical Sciences, The University of Tokyo
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HAMASHIMA Yoshitaka
Graduate School of Pharmaceutical Sciences, The University of Tokyo
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Takamura Masahiro
Graduate School Of Pharmaceutical Sciences The University Of Tokyo
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Hamashima Yoshitaka
Graduate School Of Pharmaceutical Sciences The University Of Tokyo
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