Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5‐cyclooctadiene)₂] and 1,1′‐bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu₄NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu₄NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η³‐allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.

中文翻译：

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五配位羧酸盐π-烯丙基镍配合物为镍催化直接醇胺化胺的关键中间体

通过添加n Bu ₄ NOAc和分子筛，可以有效地增强由[Ni（1,5-环辛二烯）₂ ]和1,1'-双（二苯基膦基）二茂铁构成的体系催化的伯胺和仲胺对烯丙基醇的直接胺化作用。得到高产率的相应烯丙基胺，对伯胺具有高的单烯丙基化选择性，对单取代的烯丙基醇具有高的区域选择性。的如此显着加性效应Ñ卜₄ NOAC通过分离和表征一些镍配合物，表现中性电荷的五配位η的关键作用阐明³与较早在烯丙基取代反应中报道的常见阳离子四配位复合物相反，本系统中的乙酸烯丙基乙酸酯络合物。