Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study,ACS Catalysis

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Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-03-18 , DOI: 10.1021/acscatal.0c00393
Alessandro Bismuto ₁ , Tristan Delcaillau ₁ , Patrick Müller ₁ , Bill Morandi ₁

Affiliation

Herein, we report a nickel–1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald–Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)–nickel(II) pathway for this transformation and revealed the oxidative addition complex as the resting state of the catalytic cycle. All the isolated intermediates have proven to be catalytically and kinetically competent catalysts for this transformation. The fleeting transmetalation intermediate has been successfully synthesized through an alternative synthetic organometallic pathway at lower temperature, allowing for in situ NMR study of the C–N bond reductive elimination step. This study addresses key factors governing the mechanism of the nickel-catalyzed Buchwald–Hartwig amination process, thus improving the understanding of this important class of reactions.

中文翻译：

镍催化的芳基硫醚的胺化：合成和机理的综合研究。

在本文中，我们报道了镍1,2,2-双（二环己基膦基）乙烷（dcype）配合物用于芳基硫醚的Buchwald-Hartwig催化胺化。该方案显示了在催化条件下可耐受的各种不同官能团的广泛适用性。广泛的有机金属和动力学研究支持这种转化的镍（0）-镍（II）途径，并揭示了氧化加成配合物是催化循环的静止状态。已证明所有分离出的中间体都是这种转化的催化和动力学催化剂。通过在较低的温度下通过另一种合成的有机金属途径，已经成功合成了短暂的重金属化中间体，从而可以对C–N键的还原消除步骤进行原位NMR研究。

更新日期：2020-04-23

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