Chemoselective Cleavage and Transamidation of Tertiary p-Methoxybenzyl Amides under Metal-Free Photoredox Catalysis

Hee-Chan Jeong; Hyo-Jun Lee; Keiji Maruoka

doi:10.1021/acs.orglett.4c03485

Chemoselective Cleavage and Transamidation of Tertiary p-Methoxybenzyl Amides under Metal-Free Photoredox Catalysis

Org Lett. 2024 Oct 21. doi: 10.1021/acs.orglett.4c03485. Online ahead of print.

Authors

Hee-Chan Jeong¹, Hyo-Jun Lee¹, Keiji Maruoka^{2

3}

Affiliations

¹ School of Advanced Science and Technology, Kunsan National University, Gunsan 54150, Republic of Korea.
² Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo, Kyoto 606-8501, Japan.
³ School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China.

PMID: 39431889
DOI: 10.1021/acs.orglett.4c03485

Abstract

A metal-free and mild cleavage of tertiary p-methoxybenzyl amides (PMB tert-amide) under photoredox conditions is developed using Mes-Acr-Ph⁺BF₄^- and Selectfluor to activate the electron-rich benzylic C-H bond of the PMB moiety. The resulting acyl fluoride intermediate is versatile and facilitates a one-pot transamidation of the PMB tert-amide. The value of this protocol is highlighted by performing the chemoselective activation of the PMB tert-amide in bifunctional molecules containing more reactive functionalities than the amide.