Date of Award

2015

Degree Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry

Department

Chemistry

First Advisor

Brenton L. DeBoef

Abstract

The synthesis of carbon-nitrogen (C-N) bonds is an area of research that has garnered significant interest due to the ubiquity of C-N bonds in pharmaceuticals and natural products. Various methods exist for forming C-N bonds, most recognizably Buchwald-Hartwig amination, but these reactions typically require functionalization of either the C-H or N-H bond resulting in the formation of harmful byproducts. As a result, the need to explore alternative means for synthesizing C-N bonds merits consideration. An alternative means for achieving C-N bond formation lies in the oxidative cross coupling of carbon-hydrogen (C-H) and nitrogen-hydrogen (N-H) bonds. While this approach eliminates the necessity for the prefunctionalization of CH and N-H bonds, reactions employing oxidative cross coupling can be plagued with poor regioselectivity. As a result, the use of directing groups and transition metal catalysis is typically employed to circumvent this issue. The primary focus of this dissertation is the discussion of newly developed methodologies that enhance the regioselective control of oxidative C-N bond formation. Chapters one and two detail the use of hypervalent iodine in conjunction with a transition metal catalyst to help govern the site of amination on various electron-rich, and moderately deactivated, arene systems. Chapters three and four will deviate from C—N bond forming methodologies and instead discuss synthetic routes for the construction of a molecular probe targeting the D2 receptor and the development of an amino acid coupling protocol to be utilized in the organic teaching laboratory.

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