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Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer

Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer
Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer
Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones.
density functional calculations, flow chemistry, radicals, rearrangments, small ring systems
1433-7851
4531-4534
Gonçalves, Théo P.
bf763652-dc7b-4f8e-9cc2-6be930274533
Mohamed, Mubina
f564fdda-ede9-49b8-8689-2e9fe1a90fa8
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Sneddon, Helen F.
33850179-8489-433a-b8c9-09536a4e2b18
Harrowven, David C.
bddcfab6-dbde-49df-aec2-42abbcf5d10b
Gonçalves, Théo P.
bf763652-dc7b-4f8e-9cc2-6be930274533
Mohamed, Mubina
f564fdda-ede9-49b8-8689-2e9fe1a90fa8
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Sneddon, Helen F.
33850179-8489-433a-b8c9-09536a4e2b18
Harrowven, David C.
bddcfab6-dbde-49df-aec2-42abbcf5d10b

Gonçalves, Théo P., Mohamed, Mubina, Whitby, Richard J., Sneddon, Helen F. and Harrowven, David C. (2015) Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer. Angewandte Chemie International Edition, 54 (15), 4531-4534. (doi:10.1002/anie.201411334). (PMID:25694299)

Record type: Article

Abstract

Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones.

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e-pub ahead of print date: 18 February 2015
Published date: 7 April 2015
Keywords: density functional calculations, flow chemistry, radicals, rearrangments, small ring systems
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 389695
URI: https://eprints.soton.ac.uk/id/eprint/389695
ISSN: 1433-7851
PURE UUID: fd9046b2-d7c1-4157-b031-2ce6767f8cb0
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502
ORCID for David C. Harrowven: ORCID iD orcid.org/0000-0001-6730-3573

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Date deposited: 14 Mar 2016 10:22
Last modified: 10 Sep 2019 00:57

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