Direct amidation of metallaaromatics: access to N-functionalized osmapentalynes via a 1,5-bromoamidated intermediate

Hongjian Wang; Yonghong Ruan; Yu-Mei Lin; Haiping Xia

doi:10.1039/d1sc01571k

Direct amidation of metallaaromatics: access to N-functionalized osmapentalynes via a 1,5-bromoamidated intermediate

Chem Sci. 2021 Apr 7;12(18):6315-6322. doi: 10.1039/d1sc01571k.

Authors

Hongjian Wang¹, Yonghong Ruan¹, Yu-Mei Lin¹, Haiping Xia^{1

2}

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 China linyum@xmu.edu.cn hpxia@xmu.edu.cn.
² Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology Shenzhen 518055 China.

Abstract

The direct C-H amidation or imidation of metallaaromatics with N-bromoamides or imides has been achieved under mild conditions and leads to the formation of a family of N-functionalized metallapentalyne derivatives. A unique 1,5-bromoamidated species has been identified, and can be viewed as a σ^H-adduct intermediate in a nucleophilic aromatic substitution. The 1,5-addition of both electrophilic and nucleophilic moieties into the metallaaromatic framework demonstrates a novel pathway in contrast to the typical radical process of arene C-H amidation involving N-haloamide reagents.