title: Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification.
abstract: Lyngbyaloside C, a classic macrolide, isolated from Lyngbya bouilloni, has shown moderate anticancer activity against several cancer cell lines. Here, we report the first total synthesis and stereochemical configuration reassignment of lyngbyaloside C. The synthesis highlights a one-pot intermolecular ketene esterification reaction to form the crucial tertiary ester and tetrahydropyran. In addition, a novel and concise synthetic pathway towards the 1,3-syn secondary, tertiary diol fragment is described using a regio- and stereospecific electrophilic ether transfer reaction.
authors.affiliation: Warren Family Research Center for Drug Discovery and Development and the Department of Chemistry & Biochemistry, 250 Nieuwland Science Hall, University of Notre Dame, Notre Dame, IN 46556-5670 (USA).
authors.forename: Chia-Fu
authors.initials: CF
authors.lastname: Chang
authors.affiliation: Warren Family Research Center for Drug Discovery and Development and the Department of Chemistry & Biochemistry, 250 Nieuwland Science Hall, University of Notre Dame, Notre Dame, IN 46556-5670 (USA).
authors.forename: Eric
authors.initials: E
authors.lastname: Stefan
authors.affiliation: Warren Family Research Center for Drug Discovery and Development and the Department of Chemistry & Biochemistry, 250 Nieuwland Science Hall, University of Notre Dame, Notre Dame, IN 46556-5670 (USA). taylor.61@nd.edu.
authors.forename: Richard E
authors.initials: RE
authors.lastname: Taylor
mesh_terms: D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry*; D000458:Cyanobacteria / Q000737:chemistry*; D004951:Esterification; D005030:Ethylenes / Q000138:chemical synthesis / Q000737:chemistry*; D006801:Humans; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D018942:Macrolides / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D005030:Ethylenes; D007659:Ketones; D018942:Macrolides; C576098:lyngbyaloside C; C008223:ketene
keywords: electrophilic ether transfer; ketene; lyngbyaloside C; natural products; polyketides; total synthesis