On the Superior Activity of In(I) versus In(III) Cations Towards ortho-C-Alkylation of Anilines and Intramolecular Hydroamination of Alkenes.,The Journal of Organic Chemistry

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On the Superior Activity of In(I) versus In(III) Cations Towards ortho-C-Alkylation of Anilines and Intramolecular Hydroamination of Alkenes.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-09-22 , DOI: 10.1021/acs.joc.0c01585
Zhilong Li ₁ , Shengwen Yang _{1,

2} , Guillaume Thiery ₁ , Vincent Gandon _{1,

2} , Christophe Bour ₁

Affiliation

An efficient ortho-C-alkylation of unprotected anilines with a variety of styrenes and alkenes using a univalent cationic indium(I) catalyst is reported. Mechanistic studies revealed that the reaction likely proceeds via a tandem hydroamination/Hofmann–Martius rearrangement. The high compatibility between the cationic indium(I) complex and primary anilines led us to develop an In(I)⁺-catalyzed hydroamination of alkenes using unprotected primary and secondary alkenylamines. Computations support the catalytic activity of naked In(I)⁺ ions, with an outer sphere mechanism for the C–N bond formation and a potentially inner sphere protodemetallation.

中文翻译：

关于In（I）与In（III）阳离子对苯胺的邻C-烷基化和烯烃的分子内加氢胺的优越活性。

一种有效的邻- Ç与各种使用一价阳离子铟苯乙烯和烯烃的未受保护的苯胺的烷基化报告（I）的催化剂。机理研究表明，该反应可能是通过串联加氢胺化/霍夫曼-马修斯重排而进行的。阳离子铟（I）配合物与伯苯胺之间的高度相容性使我们开发了使用未保护的伯和仲烯基胺进行In（I）⁺催化的烯烃加氢胺化反应。计算支持裸In（I）⁺离子的催化活性，并具有形成C–N键的外球机理和潜在的内球原金属化。

更新日期：2020-10-17

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