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Dual nickel- and photoredox-catalyzed enantioselective desymmetrization of meso anhydrides and C-O bond activation via phosphines and photoredox catalysis

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dc.contributor.authorStache, Erin Elizabeth, author
dc.contributor.authorRovis, Tomislav, advisor
dc.contributor.authorDoyle, Abigail G., advisor
dc.contributor.authorChen, Eugene, committee member
dc.contributor.authorMcNally, Andy, committee member
dc.contributor.authorReynolds, Melissa, committee member
dc.contributor.authorKipper, Matt, committee member
dc.date.accessioned2018-09-10T20:04:32Z
dc.date.available2018-09-10T20:04:32Z
dc.date.issued2018
dc.description.abstractDescribed herein is the application of photoredox catalysis in the development of new synthetic methods. A dual nickel- and photoredox catalyzed desymmetrization of meso succinic anhydrides was developed to generate stereodefined cis keto-acids in high enantioselectivity and diastereoselectivity. The approach employed benzylic radicals as a coupling partner, generated from a photoredox catalyzed single-electron oxidation of benzylic trifluoroborates using an inexpensive organic dye. A unique epimerization event was discovered and the degree of epimerization was rendered tunable by changing catalyst loadings to ultimately form the trans diastereomer preferentially in high enantioeselectivity. A method for the C–O bond activation of aliphatic alcohols and carboxylic acids was developed using phosphines and photoredox catalysis. This novel reaction platform was used to generate aliphatic or acyl radicals directly from benzylic alcohols and aliphatic and aromatic acids, and with terminal hydrogen atom transfer, afforded the desired deoxygenated alkanes and aldehydes. Additionally, the intermediate acyl radicals could be intercepted in an intramolecular cyclization reaction to generate new lactones, amides and ketones.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierStache_colostate_0053A_14913.pdf
dc.identifier.urihttps://hdl.handle.net/10217/191328
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2000-2019
dc.rightsCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.
dc.subjectnickel catalysis
dc.subjectphotochemistry
dc.subjectorganic synthesis
dc.subjectasymmetric catalysis
dc.titleDual nickel- and photoredox-catalyzed enantioselective desymmetrization of meso anhydrides and C-O bond activation via phosphines and photoredox catalysis
dc.typeText
dcterms.rights.dplaThis Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
thesis.degree.disciplineChemistry
thesis.degree.grantorColorado State University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy (Ph.D.)

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