title: Stereochemical determination of the leupyrrins and total synthesis of leupyrrin A1.
abstract: The stereochemical determination of the potent antifungal agents leupyrrin A1 and B1 and the total synthesis of leupyrrin A1 are reported. The relative and absolute configuration was determined by a combination of high field NMR studies, molecular modeling, and chemical derivatization. The expedient total synthesis involves a one-pot sequential Zr-mediated oxidative diyne-cyclization/regioselective opening sequence for preparation of the unique dihydrofuran ring, a highly stereoselective one-pot approach to the butyrolactone, a challenging sp(2)-sp(3) Suzuki coupling and a high-yielding Shiina macrolactonization.
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Daniel
authors.initials: D
authors.lastname: Herkommer
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Thiede
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Paul R
authors.initials: PR
authors.lastname: Wosniok
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Sandra
authors.initials: S
authors.lastname: Dreisigacker
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Maoqun
authors.initials: M
authors.lastname: Tian
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Debnar
authors.affiliation: ‡Microbial Drugs, Helmholtz Centre for Infection Research (HZI), Inhoffenstr. 7, D-38124 Braunschweig, Germany.
authors.forename: Herbert
authors.initials: H
authors.lastname: Irschik
authors.affiliation: †Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
authors.forename: Dirk
authors.initials: D
authors.lastname: Menche
mesh_terms: D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D000935:Antifungal Agents / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D003500:Cyclization; D008958:Models, Molecular; D008968:Molecular Conformation; D009231:Myxococcales / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D015040:Zirconium / Q000737:chemistry
chemical_list: D000935:Antifungal Agents; C481579:leupyrrin A1; D015040:Zirconium; D015107:4-Butyrolactone