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A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen

A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen
A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen
Oxidations with molecular oxygen are ubiquitous processes in biological systems where cofactor-dependent enzymes activate either oxygen or hydrogen peroxide to induce multichannel pathways. In stark contrast, such slow atmospheric oxidations are seldom harnessed in chemical synthesis and analysis. The present study unveils an unusual aerobic oxidation of a mesoionic dipole leading easily to a more functionalized skeleton. Although the synthetic scope has not been explored, two key considerations emerge from this transformation, as it proceeds with complete diastereoselection and could be successfully extrapolated to structurally related mesoionic chirons without racemization. How this oxidation actually occurs proved to be puzzling from the onset and only high-level computation reveals a cascade transformation, whose results reconcile theory and experiment. Hopefully, the mechanistic insights should help us to understand better the autoxidative reactions of organic molecules.
1477-0520
6328-6339
García de la Concepción, Juan
d8ca3ced-6c21-4c16-82e8-9b50611f4dc1
Ávalos, Martín
2d0b39c7-15a3-4f90-bdfb-8e4b6e69c64a
Jiménez, José L.
074cc8fd-9ea1-41fc-b8b6-551d26e5fcd3
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
García de la Concepción, Juan
d8ca3ced-6c21-4c16-82e8-9b50611f4dc1
Ávalos, Martín
2d0b39c7-15a3-4f90-bdfb-8e4b6e69c64a
Jiménez, José L.
074cc8fd-9ea1-41fc-b8b6-551d26e5fcd3
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161

García de la Concepción, Juan, Ávalos, Martín, Jiménez, José L., Cintas, Pedro and Light, Mark (2020) A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen. Organic & Biomolecular Chemistry, 18 (32), 6328-6339. (doi:10.1039/D0OB01428A).

Record type: Article

Abstract

Oxidations with molecular oxygen are ubiquitous processes in biological systems where cofactor-dependent enzymes activate either oxygen or hydrogen peroxide to induce multichannel pathways. In stark contrast, such slow atmospheric oxidations are seldom harnessed in chemical synthesis and analysis. The present study unveils an unusual aerobic oxidation of a mesoionic dipole leading easily to a more functionalized skeleton. Although the synthetic scope has not been explored, two key considerations emerge from this transformation, as it proceeds with complete diastereoselection and could be successfully extrapolated to structurally related mesoionic chirons without racemization. How this oxidation actually occurs proved to be puzzling from the onset and only high-level computation reveals a cascade transformation, whose results reconcile theory and experiment. Hopefully, the mechanistic insights should help us to understand better the autoxidative reactions of organic molecules.

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Revised-Ms-OB2020-001428 - Accepted Manuscript
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More information

Accepted/In Press date: 31 July 2020
e-pub ahead of print date: 31 July 2020
Published date: 28 August 2020

Identifiers

Local EPrints ID: 443513
URI: http://eprints.soton.ac.uk/id/eprint/443513
ISSN: 1477-0520
PURE UUID: 71ea2c4b-020d-4000-a31b-c7641d45d6ce
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 27 Aug 2020 16:31
Last modified: 26 Nov 2021 07:18

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Contributors

Author: Juan García de la Concepción
Author: Martín Ávalos
Author: José L. Jiménez
Author: Pedro Cintas
Author: Mark Light ORCID iD

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