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

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

 

aState 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
bDepartment of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA. E-mail: pengliu@pitt.edu
cDepartment of Chemistry, The Pennsylvania State University, 104 Chemistry Building, University Park, PA 16802, USA. E-mail: guc11@psu.edu

Chem. Sci. 2017, ASAP 

DOI: 10.1039/c7sc02773g

http://pubs.rsc.org/en/content/articlepdf/2017/sc/c7sc02773g?page=search

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.