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Reductive transformations of nitroarenes catalyzed by P(III)/P(V)=O redox cycling

Author(s)
Nykaza, Trevor V.(Trevor Vincent)
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Massachusetts Institute of Technology. Department of Chemistry.
Advisor
Alexander T. Radosevich.
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MIT theses may be protected by copyright. Please reuse MIT thesis content according to the MIT Libraries Permissions Policy, which is available through the URL provided. http://dspace.mit.edu/handle/1721.1/7582
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Abstract
Nitroaromatics are widely available synthetic building blocks which present a strategical opportunity to serve as direct precursors to nitrogen-containing molecules of increasing complexity and worth through reductive/deoxygenative methods. Trivalent phosphorus compounds are valuable stoichiometric reagents for a range of reductive O-atom transfer reactions involving the conversion of R₃P[superscript III] to R₃P[superscript V]=O (including nitroarene deoxygenation), but can suffer from instability, pyrophoricity, and difficulty of removal during purification for both the phosphine and the generated phosphine oxide. Having the ability to start with a bench-stable phosphine oxide--which most often is regarded as a waste by-product--and repeatedly generate an active phosphine species in situ for catalytic reaction chemistry is a motivating concept with potentially practical benefits. With the incorporation of a hydrosilane reductant, it is demonstrated that a small-ring cyclic phosphine oxide can be quickly reduced in situ to catalyze the intramolecular cyclization of o-functionalized nitrobenzene derivatives to produce nitrogen-containing heterocycles (2H-indazoles, 2H-benzotriazoles, carbazoles, indoles, and benzimidazoles), as well as the intermolecular C-N cross coupling of nitroarenes with boronic acids through exhaustive nitro deoxygenation via P[superscript III]/P[superscript V]=O catalysis. The work herein not only describes the discovery of new organocatalytic methods founded on the use of a designer, small-ring phosphine oxide (pre)catalyst (1,2,2,3,4,4-hexamethylphosphetane 1-oxide) for the reductive transformations of nitroarenes, but also details investigations into the reaction mechanism for both reductive cyclization and C-N coupling reactions.
Description
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2020
 
Cataloged from the PDF of thesis. "February 2020."
 
Includes bibliographical references.
 
Date issued
2020
URI
https://hdl.handle.net/1721.1/128071
Department
Massachusetts Institute of Technology. Department of Chemistry
Publisher
Massachusetts Institute of Technology
Keywords
Chemistry.

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