Directing group assisted para-selective C–H alkynylation of unbiased arenes enabled by rhodium catalysis,Chemical Science

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Directing group assisted para-selective C–H alkynylation of unbiased arenes enabled by rhodium catalysis
Chemical Science ( IF 7.6 ) Pub Date : 2023-09-20 , DOI: 10.1039/d3sc03528j
Uttam Dutta ₁ , Gaurav Prakash ₁ , Kirti Devi ₁ , Kongkona Borah ₁ , Xinglong Zhang ₂ , Debabrata Maiti ₁

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Regioselective C–H alkynylation of arenes via C–H activation is challenging yet a highly desirable transformation. In this regard, directing group assisted C(sp²)–H alkynylation of arenes offers a unique opportunity to ensure precise regioselectivity. While the existing methods are mainly centered around ortho-C–H alkynylation and a few for meta-C–H alkynylation, the DG-assisted para-selective C–H alkynylation is yet to be reported. Herein we disclose the first report on Rh-catalyzed para-C–H alkynylation of sterically and electronically unbiased arenes. The para-selectivity is achieved with the assistance of a cyano-based directing template and the selectivity remained unaltered irrespective of the steric and electronic influence of the substituents. The post-synthetic modification of synthesized para-alkynylated arenes is also demonstrated. The mechanistic intricacies of the developed protocol are elucidated through experimental and computational studies.

中文翻译：

通过铑催化实现无偏芳烃的指导基团辅助对位选择性C-H炔基化

通过C -H 激活对芳烃进行区域选择性 C-H 炔基化是具有挑战性的，但却是一种非常理想的转化。在这方面，指导基团辅助的芳烃 C(sp ² )–H 炔基化提供了确保精确区域选择性的独特机会。虽然现有的方法主要集中在邻位-C-H炔基化和一些间位-C-H炔基化，但DG辅助的对位选择性C-H炔基化尚未见报道。在此，我们公开了关于 Rh 催化空间和电子无偏芳烃的对-C-H 炔基化的第一份报告。对位选择性是在基于氰基的定向模板的帮助下实现的，并且无论取代基的空间和电子影响如何，选择性都保持不变。还证明了合成的对炔基化芳烃的合成后修饰。通过实验和计算研究阐明了所开发协议的机制复杂性。

更新日期：2023-09-20

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