Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Itaru Nakamura; Mao Owada; Takeru Jo; Masahiro Terada

doi:10.3762/bjoc.14.172

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Beilstein J Org Chem. 2018 Jul 31:14:1972-1979. doi: 10.3762/bjoc.14.172. eCollection 2018.

Authors

Itaru Nakamura¹, Mao Owada², Takeru Jo², Masahiro Terada^{1

2}

Affiliations

¹ Research and Analytical Center for Giant Molecule, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578 Japan.
² Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai 980-8578 Japan.

Abstract

A cationic cobalt catalyst efficiently promoted the reaction of N-alkoxycarbonyloxyanilines at 30 °C, affording the corresponding ortho-aminophenols in good to high yields. As reported previously, our mechanistic studies including oxygen-18 labelling experiments indicate that the rearrangement of the alkoxycarbonyloxy group proceeds in [1,3]-manner. In this article, we discuss the overall picture of the cobalt-catalysed [1,3]-rearrangement reaction including details of the reaction conditions and substrate scope.

Keywords: N–O bond; anilines; cobalt catalyst; concerted reaction; rearrangement.