Asymmetric organocatalytic monofluorovinylations.

The development of highly enantio- and diastereoselective organocatalytic monofluorovinylations is presented. Based on the application of α-fluoro-β-keto-benzothiazolesulfones, the formal addition of a monofluorovinylic anion synthon to a range of acyclic and cyclic enones, as well as imines, is shown. These procedures give selective access to both E- and Z-isomers of the monofluorovinylated products, which are isolated as the pure diastereoisomers in good to excellent yields with up to 99% ee.

Mechanisms in aminocatalysis.

The mechanisms of the α-, β- and γ-functionalisations of aldehydes and α,β-unsaturated aldehydes by secondary amines are presented and discussed.

Titanocene catalyzed 4-exo cyclizations: mechanism, experiment, catalyst design.

A method for the preparation of a variety of cyclobutanes via 4-exo cyclization of radicals is presented. Radical generation is carried out by electron transfer from titanocene(III) chlorides to epoxides. The reaction relies on the acceleration of the cyclization through the use of alpha,beta-unsaturated carbonyl compounds as radical traps and the thermodynamic stabilization of the cyclobutylcarbinyl radicals through conjugation.