Degree Type


Date of Award


Degree Name

Doctor of Philosophy




Organic Chemistry

First Advisor

Levi M. Stanley


This thesis presents the development of bismuth(III) triflate-promoted conjugate additions of electron-rich heteroarenes to ,-disubstituted enones, regioselective 1,6-additions of electron-rich heteroarenes to dienones, and 1,2-addition of nucleophilic heteroarenes to progesterone, 17-hydroxyprogesterone acetate and andrenosterone. Additionally, this dissertation describes the first examples of intermolecular alkene carboacylation triggered by amide CN bond activation.

Chapter II discusses the development of catalytic conjugate additions of heteroarenes to ,-disubstituted enones. Additions of a range of heteroarene nucleophiles, including furans, indoles, pyrroles, and thiophenes to a variety of ,-disubstituted enones occur to form heteroarylated all-carbon quaternary centers in up to 90% yield. These reaction occur under mild reaction conditions in the presence of low loadings of bismuth(III) triflate.

Chapter III describes the development and optimization of bismuth(III) triflate-promoted regioselective 1,6-additions of electron-rich heteroarenes to dienones. Regioselective 1,6-additions of a range of electron-rich heteroarenes, including furan, thiophene, pyrrole, and indole nucleophiles to 3-vinyl-2-cyclohexenone occur to produce a variety of -heteroarylated, ,-disubstituted enones in up to 93% yield. The high 1,6-selectivity for these reactions is attributed to the increased steric bulk at the -position relative to the -position, and no competing 1,4-conjugate addition is observed.

Chappter IV describes 1,2-additions of heteroarenes to hormone steroids. Additions of a range of electron-rich heteroarene nucleophiles, including indoles, a pyrrole, and a thiophene, to a variety of commercially available steroids and subsequent dehydration occur to form 3-heteroarylated steroidal dienes in up to 93% yield. This atom-economical reaction sequence occurs under mild reaction conditions in the presence of catalytic bismuth triflate.

Chapter V discusses studies toward nickel-catalyzed intermolecular carboacylation of alkenes with amides and tetraarylborates. Bicyclic alkenes are readily functionalized with a variety of N-benzoyl-N-phenylbenzamides and triarylboranes, which are generated in situ from the corresponding tetraarylborates, to synthesize ketone products in up to 91% yield. This reaction manifold is initiated by activation of the amide CN bond via oxidative addition by a Ni(0) catalyst. Preliminary mechanistic studies suggest that migratory insertion precedes transmetalation, and that reductive elimination is the turnover-limiting step. These reactions occur with excellent chemoselectivity and diastereoselectivity in the absence of a directing/chelating group and further demonstrate amides as practical acyl electrophiles for alkene functionalization reactions.

Copyright Owner

Tanner Lee Metz



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File Size

141 pages