Synthetic studies towards the total synthesis of cortistatin A synthesis of the pentacyclic core of citreamicin µ and GA-ring model studies

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dc.contributor.advisorMartin, Stephen F.
dc.contributor.committeeMemberKrische, Michael J
dc.contributor.committeeMemberAnslyn, Eric V
dc.contributor.committeeMemberKerwin, Sean M
dc.contributor.committeeMemberWillson, Carlton G
dc.creatorBlumberg, Shawn Thomas
dc.creator.orcid0000-0001-5633-3398
dc.date.accessioned2016-11-10T18:15:40Z
dc.date.accessioned2018-01-22T22:31:04Z
dc.date.available2016-11-10T18:15:40Z
dc.date.available2018-01-22T22:31:04Z
dc.date.issued2016-08
dc.date.submittedAugust 2016
dc.date.updated2016-11-10T18:15:40Z
dc.description.abstractThe route to the key bicyclic intermediate was streamlined to eight steps in 16% yield, using a TMSI promoted coupling of a furan and an enone. Additionally, methodology for the selective ozonolysis of the bicyclic intermediate was developed via ozone titration. Work on the dihydroxylation step led to the discovery and development of a new pH-neutral Sharpless-style asymmetric dihydroxylation. The synthesis of pentacyclic core of citreamicin µ was accomplished in 12 steps. New methodologies were developed, including: an ortho- selective bromination of a vanillin derivative and the use of 4-(Phenylazo)diphenylamine (PDA) as an internal indicator for the acetylide coupling. The usefulness of PDA led to its development as a general all-purpose indicator for the titration of strong bases, Lewis acids and reducing agents. The discovery of (n-Bu)4NOAc as a privileged additive led to the development of new methods for the synthesis of isocoumarins and new methodology for the condensation of amino acids using LiMe4 was developed.
dc.description.departmentChemistry
dc.format.mimetypeapplication/pdf
dc.identifierdoi:10.15781/T2M902595
dc.identifier.urihttp://hdl.handle.net/2152/43723
dc.language.isoen
dc.subjectTotal synthesis
dc.subjectDihydroxylation
dc.subjectTitration
dc.subjectOzonolysis
dc.subjectConjugate addition
dc.subjectMoore rearrangement
dc.subjectHydrolysis
dc.subjectIsocoumarin
dc.subjectIsoquinolone
dc.subjectCarbonylation
dc.subjectKetone coupling
dc.subjectBromination
dc.titleSynthetic studies towards the total synthesis of cortistatin A synthesis of the pentacyclic core of citreamicin µ and GA-ring model studies
dc.typeThesis
dc.type.materialtext

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