Nucleophilic vinylic substitution in bicyclic methyleneaziridines: SNVπ or SNVσ?

A stereoselective synthesis of the monodeuterated methyleneaziridine shown allowed the stereochemical course of formal SNV-mode ring-opening with copper-based organometallics to be assigned.

Regioselective synthesis of arylsulfonyl heterocycles from bromoallyl sulfones via intramolecular Heck coupling reaction

Regioselective synthesis of sulfonyl indoles, benzofurans and benzosultams via sequential base-mediated formal vinylic substitution and intramolecular Heck coupling reaction is described.

Nucleophilic Vinyl/Allyl, CF3 and CF2α Perfluoroalkyl Groups Substitution and/or E1CB Elimination Reactions of Fluorine Atom(s) in Organofluorinated Compounds

Direct substitution and elimination reactions of the fluorine atoms of difluoromethylene CF2α groups of nonspaced perfluoroalkyl chains, CF3 groups are very difficult to achieve. But, they become feasible with fluoro-alkenes, alkynes, imines or carbonyl derivatives, for which vinylic substitution and related carbanion-mediated pathways are available. In this review, we classify the major and unique fluorine substitution/elimination and rearrangement reactions and discuss their contribution to the synthesis of heterocyclic compounds.

Selective Hydrodefluorination of Hexafluoropropene to Industrially Relevant Hydrofluoroolefins

The selective hydrodefluorination of hexafluoropropene to HFO-1234ze and HFO-1234yf can be achieved by reaction with simple group 13 hydrides of the form EH3L (E = B, Al; L = SMe2, NMe3). The chemoselectivity varies depending on the nature of the group 13 element. A combination of experiments and DFT calculations show that competitive nucleophilic vinylic substitution and addition-elimination mechanisms involving hydroborated intermediates lead to complementary selectivities.<br>

Selective Hydrodefluorination of Hexafluoropropene to Industrially Relevant Hydrofluoroolefins

The selective hydrodefluorination of hexafluoropropene to HFO-1234ze and HFO-1234yf can be achieved by reaction with simple group 13 hydrides of the form EH3L (E = B, Al; L = SMe2, NMe3). The chemoselectivity varies depending on the nature of the group 13 element. A combination of experiments and DFT calculations show that competitive nucleophilic vinylic substitution and addition-elimination mechanisms involving hydroborated intermediates lead to complementary selectivities.<br>