Synthesis of the spiroketal moiety of didemnaketal A

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dc.contributor.authorDavy, Jason Alan
dc.contributor.supervisorWulff, Jeremy Earle
dc.date.accessioned2014-12-12T23:38:53Z
dc.date.available2014-12-12T23:38:53Z
dc.date.copyright2014en_US
dc.date.issued2014-12-12
dc.degree.departmentDepartment of Chemistry
dc.degree.levelDoctor of Philosophy Ph.D.en_US
dc.description.abstractThe ascidian isolation artifact didemnaketal A is a highly oxygenated polyisoprenoid capable of inhibiting HIV-1 protease through an unusual dissociative mechanism. However, recent synthetic efforts have cast doubt on stereochemical assignments in the originally published structure. In the interest of elucidating the true structure of didemnaketal A through total synthesis, we present a strategy for rapidly accessing the putative spiroketal fragment by exploiting its latent symmetry. In a single step, double Sharpless asymmetric dihydroxylation reactions (SAD) allowed us to simultaneously set all seven stereogenic centers and assemble this complex fragment from non-chiral material. The precursor was obtainable through a racemic synthesis in which the geometric isomers of a nine-membered cyclic enone converged in a ring-opening cross metathesis reaction (ROCM).en_US
dc.description.proquestcode0490en_US
dc.description.proquestemailjdavy@uvic.caen_US
dc.description.scholarlevelGraduateen_US
dc.identifier.bibliographicCitationDavy, J.A.; Mason, J.M.; Moreau, B.; Wulff, J.E. Xanthates as Synthetic Equivalents of Oxyacyl Radicals: Access to Lactones under Tin-Free Conditions. Journal of Organic Chemistry, 2012, Vol. 77, pp. 6332-6339.en_US
dc.identifier.bibliographicCitationDavy, J.A.; Moreau, B; Wulff, J.E. Tandem Dihydroxylation / Hemiketalization / Conjugate Addition Leading to a Singly Anomeric Spiroketal. Synthesis, 2012, Vol. 44, 1854-1862.en_US
dc.identifier.urihttp://hdl.handle.net/1828/5761
dc.languageEnglisheng
dc.language.isoenen_US
dc.rights.tempAvailable to the World Wide Weben_US
dc.rights.urihttp://creativecommons.org/publicdomain/zero/1.0/*
dc.subjecttotal synthesisen_US
dc.subjectnatural producten_US
dc.subjectdidemnaketalen_US
dc.subjectspiroketalen_US
dc.subjectradical cyclizationen_US
dc.titleSynthesis of the spiroketal moiety of didemnaketal Aen_US
dc.typeThesisen_US

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