Photoinduced α-C-H Amination of Cyclic Amine Scaffolds Enabled by Polar-Radical Relay

Wongyu Lee; Dongwook Kim; Sangwon Seo; Sukbok Chang

doi:10.1002/anie.202202971

Photoinduced α-C-H Amination of Cyclic Amine Scaffolds Enabled by Polar-Radical Relay

Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202202971. doi: 10.1002/anie.202202971. Epub 2022 Apr 25.

Authors

Wongyu Lee^{1

2}, Dongwook Kim^{1

2}, Sangwon Seo^{1

2}, Sukbok Chang^{1

2}

Affiliations

¹ Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
² Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141, Republic of Korea.

PMID: 35403797
DOI: 10.1002/anie.202202971

Abstract

Herein, we report a polar-radical relay strategy for α-C-H amination of cyclic amines with N-chloro-N-sodio-carbamates. The relay is initiated by in situ generation of cyclic iminium intermediate using N-iodosuccinimide (NIS) oxidant as an initiator, which then operates through a series of polar (addition and elimination) and radical (homolysis, hydrogen- and halogen atom transfer) reactions to enable the challenging C-N bond formation in a controlled manner. A broad range of α-amino cyclic amines were readily accessed with excellent regioselectivity, and the superb applicability was further demonstrated by functionalization of biologically relevant compounds.

Keywords: Amination; Amines; Radicals; Reaction Mechanisms; Sustainability.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Amination
Amines* / chemistry
Catalysis
Hydrogen* / chemistry

Substances

Amines
Hydrogen