title: Synthesis of the azaphilones (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine utilizing (+)-sparteine surrogates in copper-mediated oxidative dearomatization.
abstract: Enantioselective syntheses of the azaphilone natural products (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine that possess the natural R-configuration at the quaternary center are reported. The syntheses were accomplished using copper-mediated asymmetric dearomatization employing bis-μ-oxo copper complexes prepared from readily available (+)-sparteine surrogates. Of note, site-selective O-methylation of a vinylogous pyridone was used to access the isoquinolin-6(7H)-one core of (+)-8-O-methylsclerotiorinamine.
authors.affiliation: Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, United States.
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Germain
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Bruggemeyer
authors.forename: Jianglong
authors.initials: J
authors.lastname: Zhu
authors.forename: Cedric
authors.initials: C
authors.lastname: Genet
authors.forename: Peter
authors.initials: P
authors.lastname: O'Brien
authors.forename: John A
authors.initials: JA
authors.lastname: Porco
mesh_terms: D001578:Benzopyrans / Q000138:chemical synthesis*; D001688:Biological Products / Q000138:chemical synthesis*; D003300:Copper / Q000737:chemistry* / Q000378:metabolism; D007546:Isoquinolines / Q000138:chemical synthesis*; D008745:Methylation; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D011728:Pyridones / Q000737:chemistry; D013034:Sparteine / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature
chemical_list: C417934:8-O-methylsclerotiorinamine; D001578:Benzopyrans; D001688:Biological Products; D007546:Isoquinolines; D011728:Pyridones; D013034:Sparteine; D003300:Copper; C101449:sclerotiorin; D010100:Oxygen