Franck Brebion

Highly diastereoselective ionic/radical domino reactions: single electron transfer induced cyclization of bis-sulfoxides.

SET oxidation of bis-sulfinyl anions has enabled the uses of bis-sulfinyl radical as a synthetic equivalent of chiral acyl and methylene radicals involved in tandem reactions leading to the enantioselective construction of various carbo- and heterocyclic derivatives.

Enantiopure alkylidene-1,1-bis-p-tolylsulfoxides as new partners in diastereoselective radical cyclizations

Enantiopure alkylidene-1,1-bis-p-tolylsulfoxides have been used as new partners in diastereoselective radical cyclizations. An efficient and highly diastereoselective 6-exo-trig cyclization was observed.

Conjugate Additions to Alkylidene Bis(Sulfoxides)

A general study on the conjugate addition of anionic nucleophiles to alkylidene bis(sulfoxides) is presented. Alkoxides gave high yielding and diastereoselective addition reactions, which could be influenced by solvents and the counteranion. Azides provided an interesting entry into sulfinyl-substituted triazoles. Organometallics, mainly copper reagents, proved also to be valuable nucleophiles, and complete inversion of the stereoselectivity was achieved in the addition reaction with the latter. Modelizations provide a rationale for the observed diastereoselectivity.

New Advances in Bis(Sulfoxides) Chemistry

Abstract The chemistry of bis(sulfoxides) is discussed from two starting materials, (Ss,Ss)-bis-p-tolylsulfinylmethane and (Ss,Ss)-bis-p-tolylsulfinyl alkylidenes. Reactions presented include Michael additions, ionic-radical crossover processes and coordination complexes formations. GRAPHICAL ABSTRACT