title: Stereopentads derived from a sequence of Mukaiyama aldolization and free radical reduction on alpha-methyl-beta-alkoxy aldehydes: a general strategy for efficient polypropionate synthesis.
abstract: In a stereodivergent manner, all 16 diastereomeric stereopentads 7-22 were synthesized starting with alpha-methyl-beta-alkoxy aldehydes 25 and 27. We designed an approach based on a sequence of a Mukaiyama aldolization with enoxysilane 24 followed by a hydrogen transfer reaction. Recent advancements concerning these reactions are described, and novel key intermediates are characterized in the aldol step. The synthesis of C(1)-C(11) fragment 60 of zincophorin, which contains a synthetically challenging stereopentad unit, is described attesting the usefulness of our strategy.
authors.affiliation: Institut de recherches cliniques de Montréal, Bio-organic Chemistry Laboratory, 110 Avenue des Pins Ouest, Montréal, Québec, Canada H2W 1R7.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Brazeau
authors.forename: Philippe
authors.initials: P
authors.lastname: Mochirian
authors.forename: Michel
authors.initials: M
authors.lastname: Prévost
authors.forename: Yvan
authors.initials: Y
authors.lastname: Guindon
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005609:Free Radicals / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011422:Propionates / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D005609:Free Radicals; D011422:Propionates; C116609:3-hydroxybutanal