Exploring Diradical Chemistry: A Carbon-Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer

Théo P. Gonçalves; Mubina Mohamed; Richard J. Whitby; Helen F. Sneddon; David C. Harrowven

doi:10.1002/anie.201411334

Exploring Diradical Chemistry: A Carbon-Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer

Théo P. Gonçalves, Mubina Mohamed, Richard J. Whitby, Helen F. Sneddon, David C. Harrowven^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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.

Original language	English (US)
Pages (from-to)	4531-4534
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	15
DOIs	https://doi.org/10.1002/anie.201411334
State	Published - Apr 7 2015

Keywords

density functional calculations
flow chemistry
radicals
rearrangements
small ring systems

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201411334

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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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T2 - A Carbon-Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer

AU - Gonçalves, Théo P.

AU - Mohamed, Mubina

AU - Whitby, Richard J.

AU - Sneddon, Helen F.

AU - Harrowven, David C.

PY - 2015/4/7

Y1 - 2015/4/7

N2 - 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.

AB - 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.

KW - density functional calculations

KW - flow chemistry

KW - radicals

KW - rearrangements

KW - small ring systems

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Exploring Diradical Chemistry: A Carbon-Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer

Abstract

Keywords

ASJC Scopus subject areas

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