title: Synthesis of 8-desmethoxy psymberin: a putative biosynthetic intermediate towards the marine polyketide psymberin.
abstract: The synthesis of a putative biosynthetic precursor of psymberin including a formal synthesis of the natural product is described. The key step towards the densely functionalized tetrahydropyran core was an enantioselective catalytic Mukaiyama aldol reaction using a titanium(IV)-BINOL catalyst system. syn-Selective reduction followed by ozonolysis led to a rapid assembly of the tetrahydropyran ring. This flexible approach also allows the synthesis of similar fragments of other complex molecules such as bryostatins and pederins. The syn-selective coupling between the tetrahydropyran and the aromatic aldehyde was achieved using a boron-mediated aldol reaction which was followed by further transformations to complete the synthesis of the precursor as well as the formal synthesis of the natural product.
authors.affiliation: Institut für Bioorganische Chemie der Universität Düsseldorf im Forschungszentrum Jülich, Stetternicher Forst, 52426 Jülich, Germany.
authors.forename: Max
authors.initials: M
authors.lastname: Bielitza
authors.forename: Jörg
authors.initials: J
authors.lastname: Pietruszka
mesh_terms: D000438:Alcohols; D000447:Aldehydes / Q000737:chemistry; D000577:Amides / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis; D002384:Catalysis; D003374:Coumarins / Q000138:chemical synthesis*; D015394:Molecular Structure
chemical_list: D000438:Alcohols; D000447:Aldehydes; D000577:Amides; D001688:Biological Products; D003374:Coumarins; C498383:psymberin