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NOVEL NUCLEOPHILIC AND ELECTROPHILIC FLUOROALKYLATION
REACTIONS AND RELATED CHEMISTRY
by
Sujith Chacko
A Dissertation Presented to the
FACULTY OF THE GRADUATE SCHOOL
UNIVERSITY OF SOUTHERN CALIFORNIA
In Partial Fulfillment of the
Requirements for the Degree
DOCTOR OF PHILOSOPHY
(CHEMISTRY)
May 2008
Copyright 2008 Sujith Chacko
Object Description
| Title | Novel nucleophilic and electrophilic fluoroalkylation reactions and related chemistry |
| Author | Chacko, Sujith |
| Author email | chacko@usc.edu |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry |
| School | College of Letters, Arts and Sciences |
| Date defended/completed | 2008-03-05 |
| Date submitted | 2008 |
| Restricted until | Unrestricted |
| Date published | 2008-04-10 |
| Advisor (committee chair) | Prakash, G.K. Surya |
| Advisor (committee member) |
Olah, George A. Shing, Catherine |
| Abstract | This dissertation describes the development of new methodologies for nucleophilic monofluoromethylation, electrophilic difluoromethylation, ipsohydorxylation, nucleophilic addition reactions and synthesis of polymeric nanospheres.; Chapter 1 summarizes a brief history of organofluorine chemistry with the emphasis on application of organofluorine compounds and novel methodologies developed for introducing fluorine in organic compounds.; Chapter 2 describes a new, efficient Mitsunobu reaction using fluorinated carbon pronucleophile for the facile synthesis of monofluoromethyl derivatives of alcohols. This reaction performed under mild conditions is found to be highly feasible for primary, secondary, allylic, benzylic and alicyclic alcohols and excellent enantioselectivity is observed for chiral alcohols.; Chapter 3 deals with the synthesis of S-(difluoromethyl)diphenylsulfonium and its use as a convenient electrophilic difluoromethylating reagent for various oxygen, nitrogen and phosphorus nucleophiles.; Chapter 4 includes the synthesis of first solid-phase bound electrophilic difluoromethylating agent has been developed by an efficient, short, two step synthetic route from commercially available reagents. It has been shown that the reagent can be used for O-difluoromethylation of sulfonic acids and N-difluoromethylation of imidazoles affording pure product without further purification. This reagent may provide a valuable collection of molecules for pharmacological and materials screening through target and/or diversity oriented manual or automated library synthesis.; Chapter 5 expounds a milder and new technique to regioselectively transform aryl boronic acids to the corresponding phenols in excellent yields and high purity, using a solid PVD-H2O2 complex, which can be reused further for several runs. High level DFT calculations were also performed on model systems to study and understand the nature of these complexes.; Chapter 6 delineates a convenient protocol for the nucleophilic addition of alpha-fluoro-alpha-phenylsulfonyl-substituted methane derivatives to a variety of Michael acceptors such as, alpha, beta unsaturated esters, ketones, sulfone, and nitriles. This methodology has been further extended to propynoates to give the corresponding adducts in moderate yields.; Chapter 7 describes the synthesis of poly(vinylpyridine) nanospheres using an emulsifier-free emulsion polymerization technique. Poly(vinylpyridine) nanospheres were used as stable support for coating the magnetite nanoparticles by a one step adsorption from colloidal solution. |
| Keyword | fluoroalkylation; nucleophilic; electrophilic; synthesis |
| Language | English |
| Part of collection | University of Southern California dissertations and theses |
| Publisher (of the original version) | University of Southern California |
| Place of publication (of the original version) | Los Angeles, California |
| Publisher (of the digital version) | University of Southern California. Libraries |
| Type | texts |
| Legacy record ID | usctheses-m1101 |
| Rights | Chacko, Sujith |
| Repository name | Libraries, University of Southern California |
| Repository address | Los Angeles, California |
| Repository email | http://www.usc.edu/isd/libraries/services/ask_a_librarian/email/ |
| Filename | etd-Chacko-20080410 |
| Archival file | uscthesesreloadpub_Volume29/etd-Chacko-20080410.pdf |
Description
| Title | Page 1 |
| Full text | NOVEL NUCLEOPHILIC AND ELECTROPHILIC FLUOROALKYLATION REACTIONS AND RELATED CHEMISTRY by Sujith Chacko A Dissertation Presented to the FACULTY OF THE GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY (CHEMISTRY) May 2008 Copyright 2008 Sujith Chacko |
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