The development and analysis of new organic reactions in bulk solution and in microdroplets
Abstract/Contents
- Abstract
- The first portion of this thesis concerns the methodological development and mechanistic analysis of new C--H functionalization reactions. Over the past twenty years, the invention of protocols for the site-selective functionalization of sp3 C--H bonds has irrevocably altered the state of organic synthesis. Two such reactions described here are the oxidative cyclization of carboxylic acids to lactone products using Cu(OAc)2/K2S2O8 and the C--H bromination of N-methyl sulfamate esters with Rh(oct)4/NaOBr. The latter reaction proceeds via an intramolecular C--H abstraction by a transiently formed N-centered radical, allowing for the predictable functionalization of a single C--H bond among the many present in a complex molecule. The substrate scope of each of these reactions is delineated, and mechanistic analyses with both conventional physical organic experiments as well as with emerging ones, including desorption electrospray ionization-mass spectrometry (DESI-MS) and online electrospray ionization mass spectrometry (online ESI-MS), are provided. A purely mechanistic investigation of a third C--H functionalization process, the Ritter-type C--H amination of menthol with CuBr2/Selectfluor®, is also described. In addition to these experimental results, a review of C--H functionalization reactions using peroxydisulfate is included. The second portion of this thesis describes the analysis of organic reactions in microdroplets generated by electrospray ionization. It has been previously demonstrated that reactions in microdroplets generated through electrospray ionization (ESI) are often orders of magnitude faster than their counterparts in bulk solution. Sharpless and co-workers previously studied the [2σ+2σ+2π] cycloaddition of diethyl azodicarboxylate (DEAD) and quadricyclane and reported that the addition of water to the neat reagents caused an acceleration in the reaction rate, giving birth to what has been called "on-water" chemistry. This same reaction is examined in aqueous microdroplets (ca. 5 μm diameter), where the cycloaddition reaction is accelerated even further (by a factor of 10^2) compared to that of the "on-water" reaction reported previously. Furthermore, using a variety of analytical techniques, the structures of several other species that are detected in these droplet reactions are elucidated and a mechanism suggesting their formation is described. Although it is well established that microdroplets provide unique environments for a variety of chemical reactions, the mechanisms underlying this phenomenon are not fully understood. Using the nucleophilic ring-opening of limonene oxide with morpholine as a model reaction, the effects of microdroplet size and speed, electrospray voltage, and solvent on reaction progress are delineated. These variables are all shown to profoundly affect the extent of reaction "in droplet", which is accelerated by a factor of ~10^5 relative to the process in bulk.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2018 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Sathyamoorthi, Shyam |
|---|---|
| Associated with | Stanford University, Department of Chemistry. |
| Primary advisor | Zare, Richard N |
| Thesis advisor | Zare, Richard N |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Kanan, Matthew William, 1978- |
| Advisor | Burns, Noah |
| Advisor | Kanan, Matthew William, 1978- |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Shyam Sathyamoorthi. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis (Ph.D.)--Stanford University, 2018. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2018 by Shyam Sathyamoorthi
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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