Date on Senior Honors Thesis

5-2023

Document Type

Senior Honors Thesis

Degree Name

B.A.

Department

Chemistry

Author's Keywords

azanyl carbamate; electrophilic amination; nitrile synthesis; counterion exchange; Fukui indices; aminooxy

Abstract

Azanyl carbamates are an understudied, rarely-reported class of compounds in the organic chemistry literature. The azanyl carbamate moiety contains both a carbamate and an amine functional group. As such, this class of compounds features a high ratio of heteroatoms (atoms that are not carbon or hydrogen) relative to carbon: a characteristic of many natural and synthetic organic catalysts.1 Another reason we are particularly interested in azanyl carbamates is the fact that the amine is incorporated as an aminooxy group. An aminooxy group consists of an amine directly connected to an oxygen atom. The aminooxy group is of special interest to us because of its unusual electronic properties and selective reactivity toward molecules containing carbonyl groups (e.g., aldehydes and ketones). 2 For these reasons, we speculated that azanyl carbamate compounds might be used for unique and novel organic chemical transformations.

The present work on azanyl carbamates is best broken down into three categories: synthesis, application, and analysis.

The synthesis category involves the methodology and optimization we devised and employed to create two azanyl carbamate precursors, 1-(aminooxy)- N, N-dimethyl-1- oxomethanamine-Boc and N-((aminooxy)carbonyl)-N-isopropylpropan-2- amine-Boc, and four new azanyl carabamte compounds, 1-(aminooxy)- N, N-dimethyl-1- oxomethanamine•HCl, N- ((aminooxy)carbonyl)-N-isopropylpropan-2- amine•HCl, 1-(aminooxy)- N, N-dimethyl-1- oxomethanamine•OTf, and N-((aminooxy)carbonyl)-N-isopropylpropan-2- amine•OTf.

The application category focuses on experimental techniques and observations from reactions of 1-(aminooxy)- N, N-dimethyl-1- oxomethanamine•HCl and 1-(aminooxy)- N, N dimethyl-1- oxomethanamine•OTf in transforming aldehydes to nitriles and in our use of N- 6 ((aminooxy)carbonyl)-N-isopropylpropan-2- amine•HCl and N-((aminooxy)carbonyl)-N isopropylpropan-2- amine•OTf to add amino-functionality to select molecules.

Lastly, the analysis category concerns our proposed explanation as to why our azanyl carbamates perform the transformations they do under certain conditions. This category has also been bolstered by collaboration with Prof. Lee Thompson and his research group at the University of Louisville, who provided a computational chemistry perspective.

Overall, the studies and analyses described below demonstrate that it is possible to synthesize new azanyl carbamates in a straightforward and efficient manner and that these compounds can be effective in facilitating, at minimum, two organic transformations that have been traditionally difficult to accomplish under mild conditions. In a broader scope, these studies and analyses further confirm the notion that heteroatom rich molecules have strong potential to act as catalysts.

Lay Summary

Modern organic chemistry is a field that is constantly evolving in its methods and technology. From the evolution of simple substitution and elimination reactions to complex named reactions as well as the progression from simple chromatograms to more sophisticated Nuclear Magnetic Resonance (NMR) spectroscopy and tandem Gas Chromatography-Mass Spectrometry (GC-MS), organic chemists all over the world are now capable of performing analyses that past pioneers in the field could not even have fathomed. However, a few fundamental goals have remained constant through this growth and evolution: chemists continue to seek the ability to easily transform molecules into target compounds and to conduct these transformations in a way that is both time and cost effective.

Our work focused on an understudied class of compounds to help achieve this goal: azanyl carbamates. Figure 1 is a structural representation of an azanyl carbamate, which is composed of both a carbamate (dotted outline) and an amine functional group. Additionally, when an amine is directly connected to an oxygen, as in the structure below (solid outline), the functionality is termed an aminooxy group.

data:image/png;base64,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

Figure 1. Generic depiction of an azanyl carbamate. R represents the non-reactive rest of the molecule.

This functionality is interesting as it is rare to see organic compounds with four heteroatoms (i.e., atoms that are not carbon and hydrogen), as most compounds only feature one to three. It is also rare to see compounds with such high levels of reactive potential, created bythe reactive carbamate and aminooxy groups on each end of the molecule, without being chemically unstable.

Our experiments were centered on two azanyl carbamate compounds and their ability to facilitate two traditionally difficult chemical reactions: aldehyde-to-nitrile conversions and electrophilic amination (Figure 2). Aminooxy reagents in the literature have previously been shown to facilitate these reactions; however, the known reagents required heating, additives, or radical chemistry (reactive and dangerous unpaired electrons) to work properly. 2-7

data:image/png;base64,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

Figure 2. General depiction of aldehyde-to-nitrile conversion and electrophilic amination. X can represent any heteroatom.

The results from our experiments revealed that our two prototype azanyl carbamate reagents, for which we use the acronyms ADOM and EVE, successfully facilitated aldehyde to nitrile conversions and amination respectively. Additionally, these azanyl carbamates facilitated these two reactions with minimal to no additions of metal, base, acid, or radical initiators, at room or iced temperatures, and in a time efficient a relatively hands-off manner. These results could have major implications as the formed chemical types, nitriles and aminated species, are often used in pharmaceuticals, chemical industry, and even rocket fuel. 8, 9

Further studies on these compounds are needed to more fully assess their scope and mechanism of facilitation.

Download

Share

COinS