Trialkoxysilane-Induced Iridium-Catalyzed para-Selective C-H Bond Borylation of Arenes

Guodong Ju; Zhibin Huang; Yingsheng Zhao

doi:10.1038/s41467-024-47205-8

Trialkoxysilane-Induced Iridium-Catalyzed para-Selective C-H Bond Borylation of Arenes

Nat Commun. 2024 Apr 2;15(1):2847. doi: 10.1038/s41467-024-47205-8.

Authors

Guodong Ju¹, Zhibin Huang¹, Yingsheng Zhao^{2

3}

Affiliations

¹ Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
² Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China. yszhao@suda.edu.cn.
³ School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453000, China. yszhao@suda.edu.cn.

Abstract

An ideal approach for the construction of aryl boron compounds is to selectively replace a C-H bond in arenes with a C-B bond, and controlling regioselectivity is one of the most challenging aspects of these transformations. Herein, we report an iridium-catalyzed trialkoxysilane protecting group-assisted regioselective C-H borylation of arenes, including derivatives of benzaldehydes, acetophenones, benzoic acids, benzyl alcohols, phenols, aryl silanes, benzyl silanes, and multi-functionalized aromatic rings are all well tolerated and gave the para -selective C-H borylation products in a short time without the requirement of inert gases atmosphere. The site-selective C-H borylation can be adjustable by installing the developed trialkoxysilane protecting group on different functional groups on one aromatic ring. Importantly, the preparation process of the trialkoxychlorosilane is efficient and scalable. Mechanistic and computational studies reveal that the steric hindrance of the trialkoxysilane protecting group plays a key role in dictating the para-selectivity.