Photocatalytic C-F alkylation of trifluoromethyls using o-phosphinophenolate: mechanistic insights and substrate prediction

Rongrong Li; Xinzheng Yang; Wei Guan

doi:10.1039/d3cc03264g

Photocatalytic C-F alkylation of trifluoromethyls using o-phosphinophenolate: mechanistic insights and substrate prediction

Chem Commun (Camb). 2023 Aug 31;59(71):10648-10651. doi: 10.1039/d3cc03264g.

Authors

Rongrong Li^{1

2}, Xinzheng Yang^{1

2

3}, Wei Guan⁴

Affiliations

¹ State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, P. R. China. xyang@iccas.ac.cn.
² University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
³ Department of Chemistry, University of Washington, Seattle, WA 98195, USA.
⁴ Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China. guanw580@nenu.edu.cn.

PMID: 37581000
DOI: 10.1039/d3cc03264g

Abstract

Density functional theory computations reveal the radical mechanism of photocatalytic defluoroalkylation and hydrodefluorination of N-phenyl-2,2,2-trifluoromethylacetamide with o-phosphinophenolate (PO) cooperative catalysis. The energy gaps between the singlet substrate LUMOs and triplet photocatalyst SOMOs can be used as an effective "chemical descriptor" for predicting catalyst activity. Cesium formate assisted C-F bond activation is the most favorable path. A series of available organic structures are computationally predicted as potential substrates.