Mechanism of titanocene-mediated epoxide opening through homolytic substitution.
The mechanism of titanocene-mediated epoxide opening was studied by a combination of voltammetric, kinetic, computational, and synthetic methods. With the aid of electrochemical investigations the nature of a number of Ti(III) complexes in solution was established. In particular, the distribution of monomeric and dimeric Ti(III) species was found to be strongly affected by the exact steric conditions. The overall rate constants of the reductive epoxide opening were determined for the first time. These data were employed as the basis for computational studies of the structure and energies of the epoxide-titanocene complexes, the transition states of epoxide opening, and the beta-titanoxy radicals formed. The results obtained provide a structural basis for the understanding of the factors determining the regioselectivity of ring opening and match the experimentally determined values. By employing substituted titanocenes even more selective epoxide openings could be realized. Moreover, by properly adjusting the steric demands of the catalysts and the substrates the first examples of reversible epoxide openings were designed.
Gansäuer
Andreas
A
Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard Domagk Strasse 1, 53121 Bonn, Germany. andreas.gansaeuer@uni-bonn.de
Barchuk
Andriy
A
Keller
Florian
F
Schmitt
Martin
M
Grimme
Stefan
S
Gerenkamp
Mareike
M
Mück-Lichtenfeld
Christian
C
Daasbjerg
Kim
K
Svith
Heidi
H