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Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst

[Image: see text] The oxidative cleavage of C=C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzym...

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Autores principales: Huang, Zhiliang, Guan, Renpeng, Shanmugam, Muralidharan, Bennett, Elliot L., Robertson, Craig M., Brookfield, Adam, McInnes, Eric J. L., Xiao, Jianliang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8297864/
https://www.ncbi.nlm.nih.gov/pubmed/34160220
http://dx.doi.org/10.1021/jacs.1c05757
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author Huang, Zhiliang
Guan, Renpeng
Shanmugam, Muralidharan
Bennett, Elliot L.
Robertson, Craig M.
Brookfield, Adam
McInnes, Eric J. L.
Xiao, Jianliang
author_facet Huang, Zhiliang
Guan, Renpeng
Shanmugam, Muralidharan
Bennett, Elliot L.
Robertson, Craig M.
Brookfield, Adam
McInnes, Eric J. L.
Xiao, Jianliang
author_sort Huang, Zhiliang
collection PubMed
description [Image: see text] The oxidative cleavage of C=C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O(2) and oxidatively cleave C=C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O(2), with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O(2). For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn–oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O(2) activation that leads to the formation of the oxo species.
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spelling pubmed-82978642021-07-23 Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst Huang, Zhiliang Guan, Renpeng Shanmugam, Muralidharan Bennett, Elliot L. Robertson, Craig M. Brookfield, Adam McInnes, Eric J. L. Xiao, Jianliang J Am Chem Soc [Image: see text] The oxidative cleavage of C=C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O(2) and oxidatively cleave C=C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O(2), with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O(2). For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn–oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O(2) activation that leads to the formation of the oxo species. American Chemical Society 2021-06-23 2021-07-07 /pmc/articles/PMC8297864/ /pubmed/34160220 http://dx.doi.org/10.1021/jacs.1c05757 Text en © 2021 The Authors. Published by American Chemical Society Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Huang, Zhiliang
Guan, Renpeng
Shanmugam, Muralidharan
Bennett, Elliot L.
Robertson, Craig M.
Brookfield, Adam
McInnes, Eric J. L.
Xiao, Jianliang
Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst
title Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst
title_full Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst
title_fullStr Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst
title_full_unstemmed Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst
title_short Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst
title_sort oxidative cleavage of alkenes by o(2) with a non-heme manganese catalyst
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8297864/
https://www.ncbi.nlm.nih.gov/pubmed/34160220
http://dx.doi.org/10.1021/jacs.1c05757
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