title: Mild Amide-Cleavage Reaction Mediated by Electrophilic Benzylation.
abstract: An extremely mild method for amide-cleavage by using the triazine-based benzylating reagent 4-(4,6-diphenoxy-1,3,5-triazin-2-yl)-4-benzylmorpholinium trifluoromethanesulfonate (DPT-BM), which spontaneously releases benzyl cation species when being dissolved at room temperature, has been developed. O-Benzylation of the amide with DPT-BM and the subsequent hydrolysis of the resulting intermediate benzyl imidate salt afford the corresponding amine and benzyl ester, which can be converted by hydrogenolysis into a carboxylic acid under neutral conditions. O-Benzylation proceeds depending on both steric and electronic factors around the amide group. Thus, some amides have been selectively cleaved over other amides. Furthermore, intramolecular chemoselective cleavage of an amide group in the presence of an ester group was achieved. Such selective hydrolytic reactions cannot be performed with Meerwein reagents as well as under acidic or basic hydrolytic conditions.
authors.affiliation: Faculty of Pharmaceutical Sciences, Institute of Medical, Pharmaceutical, and Health Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
authors.forename: Kohei
authors.identifier: http://orcid.org/0000-0002-7857-1474
authors.initials: K
authors.lastname: Yamada
authors.affiliation: Faculty of Pharmaceutical Sciences, Institute of Medical, Pharmaceutical, and Health Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
authors.forename: Yukiko
authors.identifier: http://orcid.org/0000-0002-2106-3399
authors.initials: Y
authors.lastname: Karuo
authors.affiliation: Faculty of Pharmaceutical Sciences, Institute of Medical, Pharmaceutical, and Health Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
authors.forename: Yuichi
authors.identifier: http://orcid.org/0000-0003-1369-3670
authors.initials: Y
authors.lastname: Tsukada
authors.affiliation: Faculty of Pharmaceutical Sciences, Institute of Medical, Pharmaceutical, and Health Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan. kunisima@p.kanazawa-u.ac.jp.
authors.forename: Munetaka
authors.identifier: http://orcid.org/0000-0002-3296-490X
authors.initials: M
authors.lastname: Kunishima
keywords: amide cleavage; benzylation; carbocations; electrophilic addition