title: Stereospecific Synthesis of Fluoroalkenes by Silver-Mediated Fluorination of Functionalized Alkenylstannanes.
abstract: The known procedures for the conversion of alkenylstannanes into the corresponding fluoroalkenes suffer from largely variable yields and a limited compatibility with functional groups; most notably, protodestannation becomes a serious issue whenever protic sites are present in the substrate. Outlined in this paper is a convenient alternative with a much improved application profile, which is largely unperturbed by free alcohols and amides of all sorts. Key to success is the use of F-TEDA-PF6in combination with non-hygroscopic and bench-stable silver phosphinate (AgOP(O)Ph2) that acts as an essentially neutral, non-nucleophilic promotor and effective tin-scavenger at the same time. This new method opens many opportunities for late-stage fluorination of elaborate compounds far beyond the scope of the literature procedures, as witnessed by the preparation of a fluorinated macrolide antibiotic, a fluorinated prostaglandin derivative, and a set of fluorinated amino acid surrogates and peptide isosteres.
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Heiko
authors.initials: H
authors.lastname: Sommer
authors.affiliation: Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
authors.forename: Alois
authors.initials: A
authors.lastname: Fürstner
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D005459:Fluorides / Q000737:chemistry; D054879:Halogenation; D008968:Molecular Conformation; D010721:Phosphinic Acids / Q000737:chemistry; D012834:Silver / Q000737:chemistry*; D013237:Stereoisomerism; D014001:Tin / Q000737:chemistry; D017971:Tin Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D000475:Alkenes; D010721:Phosphinic Acids; D017971:Tin Compounds; C031525:stannane; D012834:Silver; D014001:Tin; D005459:Fluorides
keywords: fluorination; peptide isosteres; silver; tin; trans-addition