Lewis Acid/Hexafluoroisopropanol: A Promoter System for Selective ortho-C-Alkylation of Anilines with Deactivated Styrene Derivatives and Unactivated Alkenes,ACS Catalysis

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Lewis Acid/Hexafluoroisopropanol: A Promoter System for Selective ortho-C-Alkylation of Anilines with Deactivated Styrene Derivatives and Unactivated Alkenes
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-08-26 , DOI: 10.1021/acscatal.0c02959
Shengdong Wang ₁ , Guillaume Force ₁ , Régis Guillot ₁ , Jean-François Carpentier ₂ , Yann Sarazin ₂ , Christophe Bour ₁ , Vincent Gandon _{1,

3} , David Lebœuf ₄

Affiliation

Aniline derivatives are frequently encountered in molecules of industrial relevance such as dyes or antioxidants, which make the development of synthetic methods for the functionalization of these privileged structures highly sought-after. A general protocol for the hydroarylation of electronically diverse alkenes with anilines would be ideal to provide densely functionalized compounds. However, this transformation has been underexplored compared to more traditional hydroarylation of unactivated alkenes because of the significant challenges associated with the control of the selectivity and its substrate tolerance. Herein, we describe a selective, versatile, and user-friendly ortho-C-alkylation of anilines with alkenes that hinges on the beneficial combination of a Lewis acid (Ca(II)) and hexafluoroisopropanol as a solvent. This protocol allows for the extension of this transformation to highly deactivated styrenes and demonstrates a remarkable improved reactivity regarding aliphatic alkenes, styrene derivatives, and dienes. In addition, DFT computations were performed which, combined with experimental observations, suggest a nearly concerted mechanism that impart the ortho-selectivity.

中文翻译：

刘易斯酸/六氟异丙醇：苯胺与失活的苯乙烯衍生物和未活化的烯烃选择性邻-C-烷基化的促进剂体系

苯胺衍生物经常在工业相关分子中遇到，例如染料或抗氧化剂，这使得对这些特权结构功能化的合成方法的开发倍受追捧。用苯胺将电子多样的烯烃加氢芳基化的一般方案对于提供高密度官能化的化合物是理想的。然而，由于与选择性及其底物耐受性的控制相关的重大挑战，与未活化烯烃的更传统的氢芳基化相比，这种转化方法尚未得到充分的研究。在此，我们描述一种选择性的，通用的和用户友好的邻位苯胺与烯烃的-C-烷基化反应取决于路易斯酸（Ca（II））和六氟异丙醇作为溶剂的有益组合。该方案允许将这种转化扩展至高度失活的苯乙烯，并证明了有关脂族烯烃，苯乙烯衍生物和二烯的显着改善的反应性。另外，进行了DFT计算，其与实验观察相结合，提出了赋予邻位选择性的几乎协调的机制。

更新日期：2020-09-20

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