Tuning the redox properties of the titanocene(iii)/(iv)-couple for atom-economical catalysis in single electron steps

Radical-based transformations are an attractive target for the development of catalytic processes due to ease of radical generation, high functional group tolerance and selectivity of bond-forming reactions. In spite of these appealing features, the potential of radicals as key intermediates in cata...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 45; no. 2; pp. 448 - 452
Main Authors Gansäuer, A, Hildebrandt, S, Vogelsang, E, Flowers II, R. A
Format Journal Article
LanguageEnglish
Published England 01.01.2016
Subjects
Catalysis
Catalysts
Free radicals
Radicals
Single electrons
Tolerances
Transformations
Tuning
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Summary:Radical-based transformations are an attractive target for the development of catalytic processes due to ease of radical generation, high functional group tolerance and selectivity of bond-forming reactions. In spite of these appealing features, the potential of radicals as key intermediates in catalysis remains largely untapped. Herein we present recent work that exploits the innate ability of titanocene-based catalysts to undergo both oxidative addition and reductive elimination in single electron steps. We further demonstrate that tuning the redox properties of the titanocene-based catalyst can be used to develop efficient catalytic free radical processes including tetrahydrofuran synthesis, and radical arylation. A concept for the design of efficient catalytic radical reactions is outlined.
Bibliography:Sven Hildebrandt received his M.Sc. degree in chemistry from the University of Bonn in 2014. He is currently in his first year of his PhD under the supervision of A. Gansäuer. His research interest is the development of novel catalytic radical reactions.
Robert Flowers received his Ph.D. from Lehigh University and carried out postdoctoral studies under the guidance of Ned Arnett at Duke University. He is currently the Danser Distinguished Faculty Chair in Chemistry at Lehigh University. His research interests are in the areas of single electron transfer and mechanistic organic chemistry.
Elisabeth Vogelsang received her M.Sc. degree in chemistry from the University of Bonn in 2013. She is currently in her second year of her PhD under the supervision of A. Gansäuer, investigating novel synthesis routes to functionalized titanocenes.
Andreas Gansäuer obtained his PhD in the group of M. T. Reetz at the MPI für Kohlenforschung. After a postdoctoral position in the group of B. M. Trost at Stanford University he completed his habilitation with R. Brückner. He is Professor of Organic Chemistry at the University of Bonn and works on titanocene synthesis and the design of new catalytic radical reactions.
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ISSN:1477-9226
1477-9234
DOI:10.1039/c5dt03891j