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dc.contributor.advisorFrance, Stefan A.
dc.contributor.advisorMusaev, Djamaladdin G.
dc.contributor.advisorSadighi, Joseph
dc.contributor.authorMcLarney, Brett Derek
dc.date.accessioned2018-08-20T15:34:03Z
dc.date.available2018-08-20T15:34:03Z
dc.date.created2018-08
dc.date.issued2018-05-11
dc.date.submittedAugust 2018
dc.identifier.urihttp://hdl.handle.net/1853/60200
dc.description.abstractGiven the recent progress made with donor-acceptor (D-A) carbene C-H functionalization, as well as the functional diversity of acceptor-acceptor (A-A) carbenes, surprisingly little investigation has been conducted by the chemical community toward uncovering the latent potential of these species to functionalize C-H bonds under intermolecular manifolds. This thesis showcases the development of a catalytic intermolecular C(sp2)-H functionalization through the pursuit of beta,gamma-unsaturated-gamma-heteroatom carbonyl frameworks. Density functional theory (DFT) calculations provide insight that expands the scope of this method and enables the tuning of selectivity. DFT plays a more prominent role in a second project where it is used to build a chemical space map describing how the intermolecular C(sp3)-H insertion reactivity of A-A carbenes varies with the steric and electronic nature of the acceptor groups. This insight is then leveraged to discover a new synthetically useful class of A-A carbenes that utilizes intramolecular H-bonding to stabilize the intermolecular C-H insertion transition state. In a third pursuit, a dual C-H functionalization protocol is developed to access highly substituted indole building blocks from alpha-diazo-beta-keto nitrile and enol ether starting materials. Together, the advancements in this thesis provide the seed and structure for further growth in this promising field.
dc.format.mimetypeapplication/pdf
dc.language.isoen_US
dc.publisherGeorgia Institute of Technology
dc.subjectC-H functionalization
dc.subjectCarbene
dc.subjectDirhodium
dc.subjectInsertion
dc.subjectEnol ether
dc.subjectIntermolecular
dc.subjectCatalytic
dc.subjectAcceptor-acceptor
dc.subjectdiazo
dc.titleDevelopment of intermolecular C-H functionalization methods for acceptor-acceptor diazo compounds
dc.typeDissertation
dc.description.degreePh.D.
dc.contributor.departmentChemistry and Biochemistry
thesis.degree.levelDoctoral
dc.contributor.committeeMemberLiotta, Charles
dc.contributor.committeeMemberGutekunst, Will
dc.date.updated2018-08-20T15:34:03Z


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