Semester

Fall

Date of Graduation

2018

Document Type

Dissertation

Degree Type

PhD

College

Eberly College of Arts and Sciences

Department

Chemistry

Committee Chair

Jessica Hoover

Committee Co-Chair

Brian Popp

Committee Member

Brian Popp

Committee Member

Kung Wang

Committee Member

Bjorn Soderberg

Committee Member

Hanjing Tian

Abstract

Transition-metal-catalyzed decarboxylative coupling reactions have gained considerable attention over the past decade as an efficient route to form heterobiaryls. However, current methods for oxidative decarboxylative (hetero)arylation with unactivated C-H bonds have been limited by poor substrate scope, control of regioselectivity, and chemospecificity. This thesis describes the development of a new nickel-catalyzed oxidative decarboxylative coupling (ODC) with unactivated C-H bonds. The first chapter discusses the development of the new nickel-catalyzed ODC reaction to enable the coupling of a N,N'-bidentate directing group with a broad scope of heteroaromatic carboxylates and ortho-substituted benzoates, a scope that has not been achieved in previous oxidative decarboxylative coupling transformations. The following chapter is an extension of the nickel-catalyzed ODC reaction for the synthesis of heterocyclecontaining phenanthridinones. This chapter details an oxidative decarboxylative annulation with heteroaromatic carboxylates and ortho-fluorobenzoates. The final chapter describes the investigation and attempted synthesis of a proposed Ni(II) metallacycle from our catalytic cycles in the previous chapters. Synthesis of a Ni(II) metallacycle by denitrogenation of 3‐(quinolin‐8‐yl)‐3,4‐dihydro‐1,2,3‐benzotriazin‐4‐one led to an interesting azanickelacycle dimer. However, decarbonylation of a 2-(quinolin-8-yl)-2,3dihydro-1H-isoindole-1,3-dione led to the desired five-membered metallacycle. Each of these chapters represents the challenges to developing an oxidative decarboxylative arylation with unactivated C-H bonds with a first-row transition metal.

Embargo Reason

Publication Pending

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