Work

Photocatalytic Assembly of Structurally Diverse α ‐Trifluoromethyl Tertiary Amines Using Benign Nitrogen Donors

Year: 2025

Type: article

Abstract: α‐Trifluoromethyl amines are privileged motifs in drug design. Traditional assembly of α‐trifluoromethyl amines relies on harsh conditions and toxic reagents, prompting the demand for milder, atom‐economical methods. While alkene carboamination offers a modular access to diverse amines, the aminative difunctionalization of trifluoromethyl alkenes pose challenges due to facile defluorination. Herein, we report two visible light‐induced protocols for the aminative difunctionalization of α‐trifluoromethyl styrenes using benign nitrogen sources—nitriles and oximes—instead of prior toxic azides. A photoredox approach leads to the arylamination of α‐trifluoromethyl alkenes and radical oxidation, leveraging nitriles to capture benzyl carbocations, while a complementary alkylamination strategy exploits the decarboxylative decomposion of alkyl oxime esters and installs C ‐ and N ‐radicals on the double bond with regiospecificity. These two protocols constitute flexible access to diverse α‐trifluoromethyl tertiary amines under sustainable conditions. Only N 2 or CO 2 are emitted as byproducts. Scalability, broad substrate tolerance, and high yields highlight the practicality of this methodology.

Source: Advanced Synthesis & Catalysis

DOI: 10.1002/adsc.70194

Authors: Zhihong Qiu, Cong Ding, Luyang Tian, Zifeng Xu, Weihui Zheng, Hongming Jin

Institution: Nanjing University of Chinese Medicine

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: bronze

Funders: National Natural Science Foundation of China, Government of Jiangsu Province, Nanjing University of Chinese Medicine, Nanjing University

Awards: G1328941594, G3874644063, G6777188859