Anaerobic Hydroxylation of C(sp3)–H Bonds Enabled by the Synergistic Nature of Photoexcited Nitroarenes

20 December 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

A photoexcited nitroarene-mediated, anaerobic C–H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarenes, which serve as the C–H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost and atom economical due to the commercial availability of the nitroarene, the sole mediator of the reaction. Owing to the anaerobic conditions of the transformation, a noteworthy expansion in substrate scope can be obtained compared to prior reports. Mechanistic studies support that the photoexcited nitroarenes engage in successive hydrogen atom transfer and radical recombination events with hydrocarbons, leading to N-arylhydroxylamine ether intermediates. Spontaneous fragmentation of these intermediates leads to the key oxygen atom transfer products.

Keywords

Nitroarenes
Photochemistry
C–H Hydroxylation
C–H Functionalization

Supplementary materials

Title
Description
Actions
Title
Supporting Information
Description
Experimental details, optimization studies, characterization data, and NMR spectra (PDF).
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.