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Exploring Diradical Chemistry: A Carbon‐Centered Radical May Act as either an Anion or Electrophile through an Orbital Isomer
Author(s) -
Gonçalves Théo P.,
Mohamed Mubina,
Whitby Richard J.,
Sneddon Helen F.,
Harrowven David C.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201411334
Subject(s) - diradical , electrophile , chemistry , ion , aryl , thermal decomposition , photochemistry , character (mathematics) , realization (probability) , organic chemistry , catalysis , physics , alkyl , nuclear physics , singlet state , excited state , geometry , mathematics , statistics
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.