Amidative β-Scission of Alcohols Enabled by Dual Catalysis of Photoredox Proton-Coupled Electron Transfer and Inner-Sphere Ni-Nitrenoid Transfer

Hyeyun Keum; Harin Ryoo; Dongwook Kim; Sukbok Chang

doi:10.1021/jacs.3c11813

Amidative β-Scission of Alcohols Enabled by Dual Catalysis of Photoredox Proton-Coupled Electron Transfer and Inner-Sphere Ni-Nitrenoid Transfer

J Am Chem Soc. 2024 Jan 10;146(1):1001-1008. doi: 10.1021/jacs.3c11813. Epub 2023 Dec 18.

Authors

Hyeyun Keum^{1

2}, Harin Ryoo^{1

2}, Dongwook Kim^{1

2}, Sukbok Chang^{1

2}

Affiliations

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

PMID: 38109265
DOI: 10.1021/jacs.3c11813

Abstract

The photoredox/Ni dual catalysis is an appealing strategy to enable unconventional C-heteroatom bond formation. While significant advances have been achieved using this system, intermolecular C(sp³)-N bond formation has been relatively underdeveloped due to the difficulty in C(sp³)-N reductive elimination. Herein, we present a new mechanistic approach that utilizes dioxazolones as the Ni(II)-nitrenoid precursor to capture carbon-centered radicals by merging proton-coupled electron transfer (PCET) with nickel catalysis, thus forming synthetically versatile N-alkyl amides using alcohols. Based on mechanistic investigations, the involvement of (κ²-N,O)Ni(II)-nitrenoid species was proposed to capture photoredox PCET-induced alkyl radicals, thereby playing a pivotal role to enable the C(sp³)-N bond formation.