Zirconium-Catalyzed Hydroaminoalkylation of Alkynes for the Synthesis of Allylic Amines
Zirconium-Catalyzed Hydroaminoalkylation of Alkynes for the Synthesis of Allylic Amines
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DOI：
10.1021/jacs.0c10405
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发表时间：
2020-12-09
影响因子：
15
通讯作者：
Schafer, Laurel L.
中科院分区：
文献类型：
--
作者：
Bahena, Erick Nunez;Griffin, Samuel E.;Schafer, Laurel L.
报道了一种锆催化的炔烃加氢氨基烷基化反应，以原子经济的方式获得α，β，γ-取代的烯丙胺。该反应与 N-(三甲基甲硅烷基)苯甲胺和各种 N-苯甲基苯胺底物相容，后者产生烯丙胺作为唯一的有机产物。可以耐受具有吸电子和给电子取代基的各种内部炔烃。合成了该反应的模型中间体并进行了结构表征。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。这些配合物可以作为催化周转所需的内球质子分解反应的模型。
A zirconium-catalyzed hydroaminoalkylation of alkynes to access alpha,beta,gamma-substituted allylic amines in an atomeconomic 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.