Catalysis via Homolytic Substitutions with C-O and Ti-O Bonds: Oxidative Additions and Reductive Eliminations in Single Electron Steps.

In a combined theoretical and experimental study, an efficient catalytic reaction featuring epoxide opening and tetrahydrofuran formation through homolytic substitution reactions at C-O and Ti-O bonds was devised. The performance of these two key steps of the catalytic cycle was studied and could be...

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Bibliographic Details
Published in:	Journal of the American Chemical Society Vol. 131; no. 46; pp. 16989 - 17000
Main Authors:	Gansäuer, Andreas, Fleckhaus, André, Lafont, Manue Alejandre, Okkel, Andreas, Kotsis, Konstantinos, Anoop, Anakuthil, Neese, Frank
Format:	Article
Published:	American Chemical Society 11/25/2009
Subjects:	Catalysis Chemical bonds Epoxy compounds Tetrahydrofuran Oxidation-reduction reaction Electrons
Online Access:	View this record in EBSCOhost

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Summary:	In a combined theoretical and experimental study, an efficient catalytic reaction featuring epoxide opening and tetrahydrofuran formation through homolytic substitution reactions at C-O and Ti-O bonds was devised. The performance of these two key steps of the catalytic cycle was studied and could be adjusted by modifying the electronic properties of the catalysts through introduction of electron-donating or -withdrawing substituents to the titanocene catalysts. By regarding both steps as single electron versions of oxidative addition and reductive elimination, a mechanism-based platform for the design of catalysts and reagents for electron transfer reactions evolved that opens broad perspectives for further investigations.