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近年来有关受限路易斯酸碱对(FLPs)化学的研究受到了国内外的广泛关注,但有关芳香胺类FLPs的应用研究却极少涉及.本工作以硅烷作为还原剂,路易斯酸三(五氟苯基)硼(BCF)作为催化剂,用芳香胺盐酸盐代替苯胺,可一步反应实现炔烃与苯胺的催化氢胺化还原反应.研究发现,取代基较多的三乙基硅烷在反应中表现出较高的反应活性,吸电子取代基取代的端基芳炔的转化率也较给电子取代基取代的端基芳炔的转化率高.对催化反应的机理研究表明,胺盐与B(C6F5)3及硅烷反应所生成的硼氢化芳胺盐活性中间体“[Ar_2NH_2]~+[H-B(C_6F_5)_3]~-”的产生和分解速度决定着中间产物亚胺的生成和还原.
In recent years, the research on limited Lewis acid-base (FLPs) chemistry has drawn much attention both at home and abroad, but the research on the application of aromatic amines FLPs is rarely involved.In this work, silane as a reducing agent, Lewis acid tris Fluorophenyl) boron (BCF) as a catalyst with aromatic amine hydrochloride instead of aniline can be a one-step reaction alkyne and aniline catalytic hydrogenation reduction reaction was found that the more substituents triethylsilane in the reaction , The conversion rate of terminal arylalkynes substituted with electron-withdrawing substituents is also higher than that of terminal arylalkynes substituted with electron-substituted substituents.Research on the mechanism of catalytic reaction shows that the reaction of amine salts with The formation and decomposition rate of the active intermediate “[Ar_2NH_2] ~ + [HB (C_6F_5) _3] ~ - ” which is formed by the reaction of B (C6F5) 3 with silane determines the formation of intermediate imine And restore.