?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F39532%2F&rft.title=Stereocontrolled+Rhenium(VII)+Oxide-Mediated+N-Containing+Heterocycle+Formation&rft.creator=Kaigh%2C+Ian&rft.description=Piperidines+are+worthy+synthetic+targets+because+they+are+widely+represented+amongst+pharmaceuticals+and+biologically+active+molecules+in+general.++Rhenium(VII)+oxide+has+been+previously+used+by+the+Floreancig+group+for+the+ionization+of+allylic+alcohols%2C+followed+by+oxygen+nucleophile+attack+to+form+tetrahydropyrans.++This+work+further+expands+that+methodology+by+utilizing+protected+nitrogen+nucleophiles+to+form+piperidines.++Solvent+studies+determined+that+1%2C1%2C1%2C3%2C3%2C3-hexafluoroisopropanol+was+the+most+suitable+solvent+for+these+reactions.++An+array+of+protecting+groups+were+tested+to+determine+viable+protecting+group+conditions+and+in+an+attempt+to+develop+orthogonal+strategies+for+multiple+functional+group+tolerance.++Time+course+studies+elucidated+the+mechanism+of+the+reaction%2C+and+the+role+of+product+equilibration.++Stereochemical+assignments+were+complicated+by+the+NMR+peak+distortion+associated+with+the+barrier+to+rotation+in+amides%2C+which+was+a+consequence+of+using+protected+nitrogen+nucleophiles+as+starting+materials.++This+problem+was+overcome+by+using+an+easily+cleavable+protecting+group%2C+assigning+the+stereochemistry+of+the+deprotected+piperidine%2C+then+reprotecting+the+molecule+with+a+protecting+group+of+interest+to+obtain+reference+spectra+for+comparison+with+piperidine+products+obtained+by+cyclization+of+starting+materials+with+various+protecting+groups+of+interest+installed.++Several+substrates+were+prepared%2C+including+an+oxazinone+which+produced+a+bicyclic+product.&rft.date=2020-09-16&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F39532%2F19%2FKaigh%2520Final%2520ETD.pdf&rft.identifier=++Kaigh%2C+Ian++(2020)+Stereocontrolled+Rhenium(VII)+Oxide-Mediated+N-Containing+Heterocycle+Formation.++Master's+Thesis%2C+University+of+Pittsburgh.++++(Unpublished)++