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Zinc Complexes of β‐Ketoiminato Ligands as Efficient Catalysts for the Synthesis of α‐Amino Nitriles via Strecker Reaction
Asian Journal of Organic Chemistry ( IF 2.8 ) Pub Date : 2020-05-26 , DOI: 10.1002/ajoc.202000278
Suman Das 1 , Ravi Kumar 1 , Ajitrao Devadkar 1 , Tarun K. Panda 1
Affiliation  

We report the synthesis of α‐aminonitriles by one‐pot coupling reaction of aldehyde, amines and trimethylsilyl cyanide (TMSCN) using β‐ketoiminato zinc complexes as a pre‐catalyst in very good yield under mild reaction condition. Homoleptic zinc complex [{κ2‐(2,4,6‐Me3C6H2NC(Me)=CHC(Me)=O)}2Zn] (1 a ) was synthesized by the treatment of protic ligand [(2,4,6‐Me3C6H2NHC(Me)=CHC(Me)=O)] (L1H ) with potassium hydride and anhydrous zinc diiodide in 2 : 2 : 1 molar ratio in THF. Analogous reactions using [(2,6‐iPr2C6H3NHC(Me)=CHC(Me)=O)] (L2H ) and [(Ph2CHNHC(Me)=CHC(Me)=O)] (L3H ) as protic ligands, dinuclear zinc complexes [{κ3‐(2,6‐iPr2C6H3NC(Me)=CHC(Me)=O)}ZnI]2 (1 b ) and [Zn(Ph2CHNHC−(Me)=CHC(Me)=O)ZnI2] (1 c ) were obtained in good yield. Molecular structures of ligands L1H , L3H , and zinc complexes 1 a , 1 b , and 1 c were established by single‐crystal x‐ray diffraction analysis. Dinuclear zinc complexes 1 b , and 1 c exhibited high transformation, greater selectivity and broad substrate scope for the synthesis of α‐aminonitrile under mild condition. A most plausible mechanism for synthesis α‐aminonitrile is proposed based on several controlled reactions.

中文翻译:

β-酮亚胺基配体的锌配合物可作为有效催化剂通过Strecker反应合成α-氨基腈

我们报告了在温和的反应条件下,通过β-酮亚胺基锌络合物作为前催化剂,通过醛,胺和三甲基甲硅烷基氰化物(TMSCN)的单锅偶联反应合成α-氨基腈。均配型锌络合物[{ κ 2 - (2,4,6--ME 3 c ^ 6 ħ 2 NC(Me)的= CHC(Me)的= O)} 2的Zn](1)通过质子配体的治疗合成[ (2,4,6-Me 3 C 6 H 2 NHC(Me)= CHC(Me)= O)](L 1 H)与氢化钾和无水二碘化锌在THF中的摩尔比为2:2:1。使用[(2,6-i Pr 2 C 6 H 3 NHC(Me)= CHC(Me)= O)](L 2 H)和[(Ph 2 CHNHC(Me)= CHC(Me)= O)](L 3 H)作为质子配体,双核锌络合物[{ κ 3 - (2,6-2 ç 6 ħ 3 NC(Me)的= CHC(Me)的= O)} ZnI] 2图1b)和[锌(PH 2 CHNHC-以良好的产率获得(Me)= CHC(Me)= O)ZnI 2 ](1c)。配体L 1 HL的分子结构通过单晶X射线衍射分析建立了3 H和锌络合物1a 1b1c。双核锌配合物1b1c在温和条件下显示出高转化率,更高的选择性和广泛的底物范围,可用于合成α-氨基腈。基于几种受控反应,提出了一种最合理的合成α-氨基腈的机理。
更新日期:2020-05-26
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