title: Asymmetric organocatalytic monofluorovinylations.
abstract: 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. Furthermore, the application of this concept for the formation of highly enantioenriched bicylic compounds containing a monofluorovinyl moiety is also described. In addition, a mechanistic rationale for the observed E:Z-selectivities is presented.
authors.affiliation: Center for Catalysis, Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
authors.forename: Christian Borch
authors.initials: CB
authors.lastname: Jacobsen
authors.forename: Martin
authors.initials: M
authors.lastname: Nielsen
authors.forename: Dennis
authors.initials: D
authors.lastname: Worgull
authors.forename: Theo
authors.initials: T
authors.lastname: Zweifel
authors.forename: Esben
authors.initials: E
authors.lastname: Fisker
authors.forename: Karl Anker
authors.initials: KA
authors.lastname: Jørgensen
mesh_terms: D002384:Catalysis; D005461:Fluorine / Q000737:chemistry*; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry; D013844:Thiazoles / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D010455:Peptides; D013450:Sulfones; D013844:Thiazoles; D014753:Vinyl Compounds; D005461:Fluorine