91681-57-1

Upstream product

• 109856-85-1 (R)-1,2-epoxydodecane 

Downstream Products

• 93426-26-7 C₂₂H₃₃F₃O₃ 

Relevant academic research and scientific papers

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 β-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.

Elucidation of the mechanism of titanocene-mediated epoxide opening by a combined experimental and theoretical approach

(Figure Presented) Steric effects govern the catalytic reductive epoxide ring opening. This is the result of combined experimental and theoretical studies, which revealed interesting features of the catalyst structure, substrate binding, transition state (see picture), and reaction energies. In light of these, highly selective conditions for the ring opening can be proposed.