Author ORCID Identifier
Semester
Summer
Date of Graduation
2024
Document Type
Dissertation
Degree Type
PhD
College
Eberly College of Arts and Sciences
Department
Chemistry
Committee Chair
Jessica M. Hoover
Committee Co-Chair
Brian V. Popp
Committee Member
Carsten Milsmann
Committee Member
Bjorn Soderberg
Committee Member
Michael Gunther
Abstract
Anilines are important structural motifs present in numerous natural products and pharmaceutically relevant compounds. Among the various synthetic strategies that have been developed, transition-metal-catalyzed cross-coupling reactions represent one of the most commonly employed methods for the formation of anilines. However, these approaches generally require pre-functionalized aryl coupling partners, and the utilization of more readily available, and structurally diverse coupling partners, such as carboxylic acids, would be desirable. Decarboxylative coupling reactions have garnered significant attention as an alternative approach to form new C-N bonds, and substantial progress has been made in this area. Nevertheless, these methods remain limited, with a predominant emphasis on the synthesis of substituted anilines rather than primary anilines.
This dissertation provides a concise overview of traditional and commonly used synthetic methods for primary aniline formation in chapter 1. It also discusses related advancements in decarboxylative amination approaches. It also highlights the different amine sources employed in those transformations. Chapter 2 details the development of a new decarboxylative amination reaction that operates under mild, metal-free conditions. The scope of this methodology is shown to encompass a broad range of aromatic and heteroaromatic carboxylic acids. Additionally, preliminary mechanistic investigations have been conducted to gain insights into the reaction pathway. The final chapter presents a broad survey of diverse sets of carboxylic acids explored under the decarboxylative amination conditions. Preliminary results indicate the successful decarboxylative amidation of α-oxo carboxylic acids, enabling the formation of primary amides under mild reaction conditions. The ability to form primary amides, which is an important motif in pharmaceuticals, under mild reaction conditions would provide an attractive method for the synthesis of new C(O)-N bonds.
Recommended Citation
Basnet, Rabina, "Room Temperature Decarboxylative Amination Reactions of Carboxylic Acids" (2024). Graduate Theses, Dissertations, and Problem Reports. 12595.
https://researchrepository.wvu.edu/etd/12595
Embargo Reason
Publication Pending