From aniline to phenol: carbon-nitrogen bond activation via uranyl photoredox catalysis

Deqing Hu; Yilin Zhou; Xuefeng Jiang

doi:10.1093/nsr/nwab156

From aniline to phenol: carbon-nitrogen bond activation via uranyl photoredox catalysis

Natl Sci Rev. 2021 Aug 20;9(6):nwab156. doi: 10.1093/nsr/nwab156. eCollection 2022 Jun.

Authors

Deqing Hu¹, Yilin Zhou¹, Xuefeng Jiang¹

Affiliation

¹ Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.

Abstract

Carbon-nitrogen bond activation, via uranyl photoredox catalysis with water, enabled the conversion of 40 protogenetic anilines, 8 N-substituted anilines and 9 aniline-containing natural products/pharmaceuticals to the corresponding phenols in an ambient environment. A single-electron transfer process between a protonated aniline and uranyl catalyst, which was disclosed by radical quenching experiments and Stern-Volmer analysis, facilitated the following oxygen atom transfer process between the radical cation of protonated anilines and uranyl peroxide originating from water-splitting. ¹⁸O labeling and ¹⁵N tracking unambiguously depicted that the oxygen came from water and amino group left as ammonium salt. The 100-fold efficiency of the flow operation demonstrated the great potential of the conversion process for industrial synthetic application.

Keywords: C−N bond activation; C−O bond formation; photoredox catalysis; uranyl cations.