A zirconium-catalyzed hydroaminoalkylation of alkynes to access α,β,γ-substituted allylic amines in an atom-economic fashion is reported. The reaction is compatible with N-(trimethylsilyl)benzylamine and a variety of N-benzylaniline substrates, with the latter giving the allylic amine as the sole organic product. Various internal alkynes with electron-withdrawing and electron-donating substituents were tolerated. Model intermediates of the reaction were synthesized and structurally characterized. Stoichiometric studies on key intermediates revealed that the open coordination sphere at zirconium, imparted by the tethered bis(ureate) ligand, is crucial for the coordination of neutral donors. These complexes may serve as models for the inner-sphere protonolysis reactions required for catalytic turnover.

中文翻译：

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锆催化的炔烃加氢氨基烷基化反应合成烯丙胺

报道了锆催化的炔烃加氢氨基烷基化以原子经济方式获得 α,β,γ-取代的烯丙胺。该反应与 N-（三甲基甲硅烷基）苄胺和多种 N-苄基苯胺底物相容，后者得到烯丙胺作为唯一的有机产物。具有吸电子和给电子取代基的各种内部炔烃是可以耐受的。合成了反应的模型中间体并对其进行了结构表征。对关键中间体的化学计量研究表明，由束缚的双（脲）配体赋予的锆的开放配位球对于中性供体的配位至关重要。这些复合物可以作为催化转化所需的内球质子分解反应的模型。