Regio- and enantioselective C-C and C-N bond formations catalyzed by amphiphilic [pi]-allyliridium C,O-benzoate complexes

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dc.contributor.advisorKrische, Michael J.
dc.contributor.committeeMemberLiu, Hung-Wen
dc.contributor.committeeMemberHull, Kami L
dc.contributor.committeeMemberRose, Michael J
dc.contributor.committeeMemberWhitman, Christian P
dc.creatorJung, Woo-Ok
dc.date.accessioned2022-06-17T21:17:28Z
dc.date.available2022-06-17T21:17:28Z
dc.date.created2022-05
dc.date.issued2022-05-02
dc.date.submittedMay 2022
dc.date.updated2022-06-17T21:17:29Z
dc.description.abstractEnantioselective nucleophilic and electrophilic allylations mediated by racemic branched allylic acetates and catalyzed by π-allyliridium C,O-benzoate complexes are described. The π-allyliridium C,O-benzoate-catalyzed reductive coupling of the commodity chemical allyl acetate with acetylenic ketones mediated by 2-propanol to form enantiomerically enriched tertiary propargyl alcohols was developed. The same π-allyliridium C,O-benzoate complexes were found to be competent catalysts for the enantioselective electrophilic allylations of secondary amines and α,α-disubstituted nitronates, delivering tertiary allylic amines and (after zinc-mediated reduction of the nitroalkane) β‑stereogenic α‑quaternary primary amines, respectively. These processes form hindered C-C and C-N bonds with complete levels of branched regioselectivity. Attempted use of linear allyl acetates in the aforesaid processes provided products hydroamination instead of the expected products of Tsuji-Trost-type allylation. As revealed by deuterium labelling studies, chelation of the iridium catalyst to the internal olefin and the acetate carbonyl played a key role in partitioning the hydroamination vs allylation pathways and directing the regioselectivity of hydroamination.
dc.description.departmentChemistry
dc.format.mimetypeapplication/pdf
dc.identifier.urihttps://hdl.handle.net/2152/114730
dc.identifier.urihttp://dx.doi.org/10.26153/tsw/41633
dc.language.isoen
dc.subjectAllylation
dc.subjectIridium
dc.titleRegio- and enantioselective C-C and C-N bond formations catalyzed by amphiphilic [pi]-allyliridium C,O-benzoate complexes
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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