Generation of Masked TiII Intermediates from TiIV Amides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation,Organometallics

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Generation of Masked TiII Intermediates from TiIV Amides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation
Organometallics ( IF 2.5 ) Pub Date : 2020-10-22 , DOI: 10.1021/acs.organomet.0c00577
Adam J Pearce ₁ , Yukun Cheng ₁ , Rachel J Dunscomb ₁ , Ian A Tonks ₁

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Simple Ti amide complexes are shown to act as sources for masked Ti^II intermediates via several pathways, as demonstrated through the investigation of a unique Ti-catalyzed nitrene-coupled transfer hydrogenation of 3-hexyne. This reaction proceeds through reduction of azobenzene by a masked Ti^II catalyst, wherein both amines and 3-hexyne can serve as the hydrogen source/reductant for Ti by forming putative titanaziridines via β-H abstraction or putative titanacyclopentynes via protonolysis, respectively.

中文翻译：

通过 β-H 抽提或炔去质子化从 TiIV 酰胺中生成掩蔽 TiII 中间体：Ti 催化的氮烯偶联转移氢化的一个例子

简单的 Ti 酰胺配合物显示出通过多种途径作为掩蔽 Ti ^II中间体的来源，如通过研究独特的 Ti 催化氮烯偶联转移氢化 3-己炔所证明的。该反应通过掩蔽的 Ti ^II催化剂还原偶氮苯进行，其中胺和 3-己炔都可以作为 Ti 的氢源/还原剂，分别通过 β-H 提取形成推定的钛氮丙啶或通过质子分解形成推定的环戊炔。

更新日期：2020-11-09

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