Dehydrogenative α-Oxygenation of Cyclic Ethers by a High-Valent Manganese(IV)-Oxo Species

Mubarak, M Qadri E, Ali, Hafiz Saqib, Zhou, Jimei, Li, Chaoqun, Xiao, Jianliang ORCID: 0000-0003-2010-247X and de Visser, Sam P (2023) Dehydrogenative α-Oxygenation of Cyclic Ethers by a High-Valent Manganese(IV)-Oxo Species. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 26 (5).

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Official URL: http://dx.doi.org/10.1002/ejic.202200621

Abstract

<jats:title>Abstract</jats:title><jats:p>High‐valent metal‐oxo species are typical catalytic cycle intermediates in mono‐oxygenases and dioxygenases and commonly react through oxygen atom transfer to substrates. In this work we study a biomimetic model complex with a 1,1’‐bis((3,5‐dimethylpyridin‐2‐yl)methyl)‐2,2’‐bipiperidine ligand system bound to a manganese(IV)‐oxo(hydroxo) species and study its formation from manganese(II)‐hydroxo and H<jats:sub>2</jats:sub>O<jats:sub>2</jats:sub>as well as its reaction with (<jats:italic>S</jats:italic>)‐1‐phenylisochromane through dehydrogenative α‐oxygenation. The work utilizes density functional theory methods to explore its catalytic cycle and its reactivity patterns. We show that the manganese(IV)‐oxo(hydroxo) species is an active oxidant and preferentially the oxo group abstracts a hydrogen atom from substrate with barriers well lower in energy than those found for hydrogen atom abstraction by the hydroxo group. Interestingly, the rate‐determining step is the OH rebound rather than the hydrogen atom abstraction, which would imply they would have limited kinetic isotope effect for the replacement of the transferring hydrogen atom by deuterium.</jats:p>

Item Type:	Article
Uncontrolled Keywords:	Biomimetic models, Hydrogen peroxide, Manganese, Oxygen atom transfer, Reaction mechanism
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	16 Feb 2023 17:28
Last Modified:	11 Dec 2023 04:34
DOI:	10.1002/ejic.202200621
Open Access URL:	https://doi.org/10.1002/ejic.202200621
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3168460