Photoredox-Catalyst-Enabled para-Selective Trifluoromethylation of tert-Butyl Arylcarbamates

Yaqiqi Jiang; Bao Li; Nana Ma; Sai Shu; Yujie Chen; Shan Yang; Zhibin Huang; Daqing Shi; Yingsheng Zhao

doi:10.1002/anie.202105631

Photoredox-Catalyst-Enabled para-Selective Trifluoromethylation of tert-Butyl Arylcarbamates

Angew Chem Int Ed Engl. 2021 Aug 23;60(35):19030-19034. doi: 10.1002/anie.202105631. Epub 2021 Jul 20.

Authors

Yaqiqi Jiang^{1

2}, Bao Li³, Nana Ma³, Sai Shu^{1

2}, Yujie Chen^{1

2}, Shan Yang^{1

2}, Zhibin Huang^{1

2}, Daqing Shi^{1

2}, Yingsheng Zhao^{1

2}

Affiliations

¹ Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.
² School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453000, P. R. China.
³ Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453000, P. R. China.

PMID: 34160867
DOI: 10.1002/anie.202105631

Abstract

The direct incorporation of a trifluoromethyl group on an aromatic ring using a radical pathway has been extensively investigated. However, the direct highly para-selective C-H trifluoromethylation of a class of arenes has not been achieved. In this study, we report a light-promoted 4,5-dichlorofluorescein (DCFS)-enabled para-selective C-H trifluoromethylation of arylcarbamates using Langlois reagent. The preliminary mechanistic study revealed that the activated organic photocatalyst coordinated with the arylcarbamate led to para-selective C-H trifluoromethylation. Ten-gram scale reaction performs well highlighting the synthetic importance of this new protocol.

Keywords: photoirradiation; site selectivity; ten gram scale; trifluoromethylation.

Abstract

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