Oxidative Cleavage of Alkenes by O₂ with a Non-Heme Manganese Catalyst

Huang, Zhiliang, Guan, Renpeng, Shanmugam, Muralidharan, Bennett, Elliot L ORCID: 0000-0003-3798-4296, Robertson, Craig M ORCID: 0000-0002-4789-7607, Brookfield, Adam, McInnes, Eric JL and Xiao, Jianliang ORCID: 0000-0003-2010-247X (2021) Oxidative Cleavage of Alkenes by O₂ with a Non-Heme Manganese Catalyst. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 143 (26). pp. 10005-10013.

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Abstract

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 O₂ 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 O₂, 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 O₂. 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 O₂ activation that leads to the formation of the oxo species.

Item Type:	Article
Uncontrolled Keywords:	Generic health relevance
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	25 Jun 2021 09:29
Last Modified:	14 Mar 2024 21:41
DOI:	10.1021/jacs.1c05757
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3127680