title: Total synthesis of the postulated structure of fulicineroside.
abstract: A total synthesis of the proposed structures of fulicineroside and its aglycone fulicinerine is reported. The tetrasubstituted dibenzofuran substructure was accessible either through a Pd-mediated ortho-metalation or by an Ir-catalyzed meta-borylation. The synthesis of the β,β,α-linked trisaccharide consisting of D-olivose, L-rhodinose, and L-rhamnose was challenged by the unprecedented β-linked rhodinose. A Pd-catalyzed β-selective glycosylation of a 4-epi-rhodinose and a subsequent Mitsunobu inversion provided selectively the β-linked L-rhodinose-L-rhamnose disaccharide. Comparison with the reported data for the natural product and the aglycone suggests a misassignment of the structure of the natural product.
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35043 Marburg, Germany.
authors.forename: Ruben
authors.initials: R
authors.lastname: Bartholomäus
authors.forename: Fabian
authors.initials: F
authors.lastname: Dommershausen
authors.forename: Markus
authors.initials: M
authors.lastname: Thiele
authors.forename: Narayan S
authors.initials: NS
authors.lastname: Karanjule
authors.forename: Klaus
authors.initials: K
authors.lastname: Harms
authors.forename: Ulrich
authors.initials: U
authors.lastname: Koert
mesh_terms: D001572:Benzofurans / Q000138:chemical synthesis* / Q000737:chemistry*; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D003837:Deoxy Sugars / Q000737:chemistry*; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D006031:Glycosylation; D014312:Trisaccharides / Q000138:chemical synthesis
chemical_list: D001572:Benzofurans; D001688:Biological Products; D003837:Deoxy Sugars; D004187:Disaccharides; D006027:Glycosides; D014312:Trisaccharides; C586374:fulicineroside; C407877:olivose; C023614:dibenzofuran