Graduate Thesis Or Dissertation
 

Application of Density Functional Theory to Exploration of Reactions

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https://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/n583z279n

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  • My work has focused on using density functional theory to elucidate mechanisms of organocatalytic and transition metal catalyzed reactions by considering competing mechanisms. In each of the three presented studies computational investigation complemented experimental work by predicting stereoselectivity or revealing origins of stereo, regio, or chemoselectivity. A study on the formation of dihydrobenzoxazin-4-ones through a N-heterocyclic carbene catalyzed reaction of aza-o-quinone methides with trifluoromethyl ketones accurately predicted enantioselectivity. An energy decomposition distortion-interaction analysis provided an insight into the origins of stereocontrol. An accompanying potential energy surface contour plot suggested a concerted [4+2] mechanism for the formal annulation. A β,β-difluoroalkyl–Pd intermediate can undergo a unimolecular β-F elimination to deliver monofluorinated alkene products or avoid a -fluoride elimination to deliver difluorinated products. In this joint experimental and computational study, a Pd/Cu co-catalyzed reaction of arylsulfonyl chlorides and gem-difluoroalkenes that proceeds through β,β-difluoroalkyl–Pd intermediate and avoids a -fluoride elimination is presented. Computations revealed that: 1) Pd facilitates the formation of a C–C bond between aryl and gem-difluoroalkene; 2) the operative mechanism involves PdIII; 3) the chemoselectivity is not influenced by the homobenzylic and benzylic positions of the H and F atoms; 4) the selectivity arises from strong preference for breaking C–H vs. C–F bond and forming of Pd–H vs. Pd–F bond. A joint experimental and computational investigation of the Pd-catalyzed reaction between allenamides, alkynes, and dimethylphenylsilyl boronic acid pinacol ester to produce 1,4-skipped dienes highlights how computations can shed light on complex multicomponent mechanisms by revealing the favored sequence of bond forming events. Computationally predicted E/Z product selectivity was confirmed by an X ray crystal structure.
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