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 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.
Gansäuer
Andreas
A
Kekule-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard Domagk Str. 1, 53121 Bonn, Germany. andreas.gansaeuer@uni-bonn.de
Fleckhaus
André
A
Lafont
Manuel Alejandre
MA
Okkel
Andreas
A
Kotsis
Konstantinos
K
Anoop
Anakuthil
A
Neese
Frank
F