Carbon-carbon bond formation via transition metal-catalyzed transfer hydrogenative carbonyl addition

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dc.contributor.advisorKrische, Michael J.
dc.contributor.committeeMemberLiu, Hung-Wen
dc.contributor.committeeMemberHull, Kami
dc.contributor.committeeMemberWhitman, Christian P
dc.creatorSpinello, Brian Joseph
dc.creator.orcid0000-0003-0208-567X
dc.date.accessioned2023-02-17T16:32:35Z
dc.date.available2023-02-17T16:32:35Z
dc.date.created2022-12
dc.date.issued2022-11-28
dc.date.submittedDecember 2022
dc.date.updated2023-02-17T16:32:36Z
dc.description.abstractCarbonyl addition persists as one of the most broadly utilized methods for the construction of carbon-carbon bonds. However, classical methods for carbonyl addition require preformed organometallic reagents, which are often highly basic, moisture sensitive, and hazardous. To circumvent these issues, novel synthetic methods have been developed for the construction of carbon-carbon bonds via metal-catalyzed transfer hydrogenative carbonyl reductive coupling, which avoid the use of stoichiometric organometallic reagents. Three methods for ketone formation are described that involve rhodium-catalyzed carbonyl reductive coupling to deliver allylic or homoallylic alcohols, which undergo immediate redox-isomerization to generate saturated ketones products. Additionally, the use of a novel iodide-bound ruthenium-JOSIPHOS catalyst system catalyzes anti-diastereo- and enantioselective carbonyl crotylations of primary alcohols mediated by methylallene and butadiene. Finally, π-allyliridium C,O-benzoate complexes catalyze enantioselective electrophilic allylation of α,α-disubstituted nitronates providing entry to β-stereogenic α-quaternary primary amines after zinc-mediated nitroalkane reduction.
dc.description.departmentChemistry
dc.format.mimetypeapplication/pdf
dc.identifier.urihttps://hdl.handle.net/2152/117490
dc.identifier.urihttp://dx.doi.org/10.26153/tsw/44370
dc.language.isoen
dc.subjectRhodium
dc.subjectRuthenium
dc.subjectIridium
dc.subjectCarbonyl addition
dc.subjectKetones
dc.subjectTransfer hydrogenation
dc.titleCarbon-carbon bond formation via transition metal-catalyzed transfer hydrogenative carbonyl addition
dc.typeThesis
dc.type.materialtext
thesis.degree.departmentChemistry
thesis.degree.disciplineChemistry
thesis.degree.grantorThe University of Texas at Austin
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy

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