Issue 15, 2022

Light-driven reduction of aromatic olefins in aqueous media catalysed by aminopyridine cobalt complexes

Abstract

A catalytic system based on earth-abundant elements that efficiently hydrogenates aryl olefins using visible light as the driving-force and H2O as the sole hydrogen atom source is reported. The catalytic system involves a robust and well-defined aminopyridine cobalt complex and a heteroleptic Cu photoredox catalyst. The system shows the reduction of styrene in aqueous media with a remarkable selectivity (>20 000) versus water reduction (WR). Reactivity and mechanistic studies support the formation of a [Co–H] intermediate, which reacts with the olefin via a hydrogen atom transfer (HAT). Synthetically useful deuterium-labelled compounds can be straightforwardly obtained by replacing H2O with D2O. Moreover, the dual photocatalytic system and the photocatalytic conditions can be rationally designed to tune the selectivity for aryl olefin vs. aryl ketone reduction; not only by changing the structural and electronic properties of the cobalt catalysts, but also by modifying the reduction properties of the photoredox catalyst.

Graphical abstract: Light-driven reduction of aromatic olefins in aqueous media catalysed by aminopyridine cobalt complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
26 11 2021
Accepted
09 3 2022
First published
14 3 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 4270-4282

Light-driven reduction of aromatic olefins in aqueous media catalysed by aminopyridine cobalt complexes

C. Casadevall, D. Pascual, J. Aragón, A. Call, A. Casitas, I. Casademont-Reig and J. Lloret-Fillol, Chem. Sci., 2022, 13, 4270 DOI: 10.1039/D1SC06608K

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