Chemo-divergent Cyano Group Migration: Involving Elimination and Substitution of the Key α-Thianthrenium Cyano Species

Bo Li; Donghui Xing; Xiaohong Li; Shunqin Chang; Huanfeng Jiang; Liangbin Huang

doi:10.1021/acs.orglett.3c02396

Chemo-divergent Cyano Group Migration: Involving Elimination and Substitution of the Key α-Thianthrenium Cyano Species

Org Lett. 2023 Sep 15;25(36):6633-6637. doi: 10.1021/acs.orglett.3c02396. Epub 2023 Sep 6.

Authors

Bo Li¹, Donghui Xing¹, Xiaohong Li¹, Shunqin Chang¹, Huanfeng Jiang², Liangbin Huang^{1

2}

Affiliations

¹ State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510640, People's Republic of China.
² Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510641, People's Republic of China.

PMID: 37672391
DOI: 10.1021/acs.orglett.3c02396

Abstract

Herein, we report a light-driven, radical-type cyano migration in the absence of a photocatalyst, enabling a chemo-divergent synthesis of (Z)-alkenyl nitriles and ketones. Trifluoromethyl thianthrenium salt (TT-CF₃⁺OTf^-) plays multiple roles: (a) absorbing light to generate trifluoromethyl radicals to initiate the reaction and (b) forming α-thianthrenium cyano species by in situ capture of TT^• ⁺. (Z)-Alkenyl nitriles were formed through the elimination of thianthrenium salts, and aryl ketones were obtained via the nucleophilic substitution of thianthrenium salts.