Total synthesis of belizentrin methyl ester: the polyhydroxylated sidechain

Größl, Sylvester

Total synthesis of belizentrin methyl ester: the polyhydroxylated sidechain

dc.contributor.advisor	Fürstner, Alois
dc.contributor.author	Größl, Sylvester
dc.contributor.referee	Krause, Norbert
dc.date.accepted	2018-10-24
dc.date.accessioned	2018-11-27T07:41:47Z
dc.date.available	2018-11-27T07:41:47Z
dc.date.issued	2018
dc.description.abstract	Herein, the first concise total synthesis of belizentrin methyl ester as a stable derivative of the natural product is described. Belizentrin was isolated as a structurally complex secondary metabolite from the marine dinoflagellate Prorocentrum belizeanum. This polyketide is a potent neurotoxin decorated with 16 stereocentres in total, comprising of a polyunsaturated macrocyclic core structure and a polyhydroxylated sugar-based sidechain. Key steps of the synthesis of the western polyhydroxylated sidechain enclosed an E-selective Wittig olefination and a Sharpless dihydroxylation aiming for the central all-syn-triol motif. The route towards its C-glucosidic core involved the preparation of a highly enolizable phosphorus ylide which could only be obtained after P-alkylation of the corresponding bromo ketone in benzene glass. The western belizentrin fragment was obtained in 17 steps (LLS) with an overall yield of 3-5% starting from the commercially available amino acid L-glutamic acid and the per-Oacetyl derivative of alpha-D-glucose. The final coupling of the western and eastern belizentrin counterparts was finally achieved via the Kocienski modification of the Julia olefination after transmetallation to zinc regarding the vulnerability of the highly base-sensitive polyene motif.	en
dc.identifier.uri	http://hdl.handle.net/2003/37810
dc.identifier.uri	http://dx.doi.org/10.17877/DE290R-19805
dc.language.iso	en	de
dc.subject	Naturstoffsynthese	de
dc.subject	Totalsynthese	de
dc.subject	Belinzentrin	de
dc.subject	Naturstoff	de
dc.subject	Neurotoxin	de
dc.subject	Kohlenhydrate	de
dc.subject	Wittig-Olefinierung	de
dc.subject	Sharpless-Dihydroxylierung	de
dc.subject.ddc	540
dc.subject.rswk	Naturstoffchemie	de
dc.subject.rswk	Synthese	de
dc.title	Total synthesis of belizentrin methyl ester: the polyhydroxylated sidechain	en
dc.type	Text	de
dc.type.publicationtype	doctoralThesis	de
dcterms.accessRights	open access
eldorado.secondarypublication	false	de

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Organische Chemie