title: An Asymmetric Redox Arylation: Chirality Transfer from Sulfur to Carbon through a Sulfonium [3,3]-Sigmatropic Rearrangement.
abstract: A general, asymmetric redox arylation of ynamides and thioalkynes with chiral sulfoxides is reported. This is the first example of a general 1,4-chirality transfer from sulfur to a carbon stereocenter through a sulfonium [3,3]-sigmatropic rearrangement. This reaction delivers α-arylated thioesters and amides under mild conditions in an atom-economical manner. The products are formed in high yields with enantiomeric ratios up to 99.5:0.5. Quantum chemical calculations suggest a mechanism for the chirality transfer from sulfur to carbon and explain the experimentally observed correlation of the enantioselectivity with both the catalyst and the substrate.
authors.affiliation: Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
authors.forename: Dainis
authors.initials: D
authors.lastname: Kaldre
authors.affiliation: Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.|Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090, Vienna, Austria.
authors.forename: Boris
authors.initials: B
authors.lastname: Maryasin
authors.affiliation: Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
authors.forename: Daniel
authors.initials: D
authors.lastname: Kaiser
authors.affiliation: Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
authors.forename: Oliver
authors.initials: O
authors.lastname: Gajsek
authors.affiliation: Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090, Vienna, Austria.
authors.forename: Leticia
authors.initials: L
authors.lastname: González
authors.affiliation: Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
authors.forename: Nuno
authors.initials: N
authors.lastname: Maulide
keywords: asymmetric synthesis; chirality transfer; rearrangement; sulfoxides; ynamides