relation: http://d-scholarship-dev.library.pitt.edu/16511/
title: Catalytic Asymmetric Bond Constructions in Complex Molecule Synthesis.  An Approach to the Synthesis of Spirolide C and the Development of Enantioselective Enolate Hydroxylation Reactions
creator: Guo, Binbin
description: The asymmetric synthesis of spirolide C, a highly potent marine toxin, has been investigated in our laboratory.  The construction of C7-C28 bis-spiroketal was completed through a strategy utilizing an intermolecular Stetter reaction and a biomimetic ketalization process.  Stereocenters were set in great diastereo- and enantioselectivity via asymmetric catalysis.  The efficiency of the synthesis was demonstrated by its convergency and high yields.     A cinchona alkaloid catalyzed ketene-oxaziridine cyclocondensation has been developed to provide an access to enantioenriched α-hydroxy carbonyl compounds.  The oxazolidinones arising from the cyclocondensation were converted to various α-hydroxy carbonyl compounds via nucleophilic ring openings.  Greater than 98% ee was achieved in oxazolidinone formation and the subsequent ring openings proceeded with retention of the ee or minor epimerization.  
date: 2013-01-25
type: University of Pittsburgh ETD
type: PeerReviewed
format: application/pdf
language: en
identifier: http://d-scholarship-dev.library.pitt.edu/16511/1/Binbin_Guo_dissertation.pdf
identifier:   Guo, Binbin  (2013) Catalytic Asymmetric Bond Constructions in Complex Molecule Synthesis. An Approach to the Synthesis of Spirolide C and the Development of Enantioselective Enolate Hydroxylation Reactions.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)