A unified photoredox-catalysis strategy for C(sp3)–H hydroxylation and amidation using hypervalent iodine

Guo-Xing Li; Cristian A. Morales-Rivera; Fang Gao; Yaxin Wang; Gang He; Peng Liu; Gong Chen

doi:10.1039/C7SC02773G

A unified photoredox-catalysis strategy for C(sp³)–H hydroxylation and amidation using hypervalent iodine†

Guo-Xing Li,^a Cristian A. Morales-Rivera,^b Fang Gao,^a Yaxin Wang,^a Gang He,^a Peng Liu

*^b and Gong Chen

*^ac

Author affiliations

* Corresponding authors

^a State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China
E-mail: gongchen@nankai.edu.cn

^b Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA
E-mail: pengliu@pitt.edu

^c Department of Chemistry, The Pennsylvania State University, 104 Chemistry Building, University Park, PA 16802, USA
E-mail: guc11@psu.edu

Abstract

We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C–H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl–OH) oxidant is critical for efficient tertiary C–H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C–H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl–OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by H₂O or CH₃CN cosolvent is presented.

This article is part of the themed collections: Celebrating 100 Years of Chemistry at Nankai University, In celebration of Chinese New Year and Most downloaded articles of 2017: Organic Chemistry

Supplementary files

Article information

DOI: https://doi.org/10.1039/C7SC02773G
Article type: Edge Article
Submitted: 21 Jūn. 2017
Accepted: 02 Sept. 2017
First published: 04 Sept. 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

Download Citation

Chem. Sci., 2017,8, 7180-7185

Permissions

Request permissions

A unified photoredox-catalysis strategy for C(sp³)–H hydroxylation and amidation using hypervalent iodine

G. Li, C. A. Morales-Rivera, F. Gao, Y. Wang, G. He, P. Liu and G. Chen, Chem. Sci., 2017, 8, 7180 DOI: 10.1039/C7SC02773G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Chemical Science