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Mechanistic Investigations of Transition Metal-Catalyzed C–C and C–O Bond Formation Reactions

Quirion, Kevin Patrick (2024) Mechanistic Investigations of Transition Metal-Catalyzed C–C and C–O Bond Formation Reactions. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

Computational chemistry techniques were applied to broaden the mechanistic understanding of various transition metal catalyzed C−C and C−O bond formation reactions. The specific experimental systems investigated include the Ni-catalyzed alkene dicarbofunctionalization with an aryl iodide and an alkyl iodide as electrophiles, inner- and outer-sphere C−C bond reductive elimination mechanisms in radical-mediated Ni catalysis, Pd-catalyzed cross-electrophile reductive coupling of two (hetero)aryl halides, carboxylative Buchwald–Hartwig amination with a dual Ni/photoredox catalyst system, and a Cu-catalyzed difluorocarbene insertion into oxirane to form difluoro-oxetanes. Density functional theory (DFT) and coupled cluster (CC) calculations were employed to investigate the reaction mechanisms and factors that control reactivity and selectivity. Several previously less explored elementary reactions were investigated, including oxidative addition of alkyl iodide with nickel complexes of different oxidation states and coordination geometry, Pd-to-Pd transmetallation within dimeric aryl Pd(II) halide species, and C−O reductive elimination from high-oxidation state Ni and Cu species. The origins of cross-electrophile selectivity in the Ni-catalyzed alkene dicarbofunctionalization and the Pd-catalyzed aryl halide reductive coupling were investigated. Further outlined is the reliance on higher oxidation states of Ni and Cu to selectively drive C−O bond formation via reductive elimination.

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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Quirion, Kevin Patrickkpq1@pitt.edukpq10000-0002-1599-9422
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairLiu, Pengpengliu@pitt.edu
Committee MemberFloreancig, Paulflorean@pitt.edu
Committee MemberWang, Yimingym.wang@pitt.edu
Committee MemberKeith, Johnjakeith@pitt.edu
Date: 27 August 2024
Date Type: Publication
Defense Date: 22 April 2024
Approval Date: 27 August 2024
Submission Date: 28 May 2024
Access Restriction: 1 year -- Restrict access to University of Pittsburgh for a period of 1 year.
Number of Pages: 124
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: DFT, density functional theory, computational chemistry, organic chemistry
Date Deposited: 27 Aug 2024 14:22
Last Modified: 27 Aug 2024 14:22
URI: http://d-scholarship.pitt.edu/id/eprint/46456

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