A diversity-oriented approach to the palladium-catalyzed modular assembly of conjugated compounds and heterocycles: high-value compounds from trichloroethylene

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dc.contributor.supervisor Hultin, Philip G. (Chemistry) en
dc.contributor.author Geary, Laina Michelle
dc.date.accessioned 2011-01-19T22:04:27Z
dc.date.available 2011-01-19T22:04:27Z
dc.date.issued 2011-01-19T22:04:27Z
dc.identifier.citation Geary, Laina M.; Hultin, Philip G. (2009). Modular Construction of Benzo[b]furans from 1,2-Dichlorovinyl Ethers, Organic Letters, 11(23): 5478-5481. en
dc.identifier.citation Geary, Laina M.; Hultin, Philip G. (2010). Palladium-Catalyzed Modular Assembly of Electron–Rich Alkenes, Dienes, Trienes and Enynes from (E)-1,2 Dichlorovinyl Phenyl Ether, Journal of Organic Chemistry 75(19):6354-6371. en
dc.identifier.citation Geary, Laina M.; Hultin Philip G. (2010) 2-Substituted Benzo[b]furans from (E)-1,2-Dichlorovinyl Ethers and Organoboron Reagents: Scope and Mechanistic Investigations into the One-Pot Suzuki Coupling/Direct Arylation, European Journal of Organic Chemistry (29):5563-5573. en
dc.identifier.uri http://hdl.handle.net/1993/4381
dc.description.abstract Trichloroethylene, a simple and very inexpensive material, has been identified as a tri- and tetrafunctionalizable building block. A combination of selective palladium-catalyzed cross-coupling reactions with standard lithiation and electrophilic quenching yields a wide variety of unsaturated linear or cyclic compounds in excellent yields in few synthetic steps. Dichlorovinyl ethers, obtained from a nucleophilic displacement reaction with trichloroethylene, are the basic starting materials. Two sets of conditions have been developed to achieve the reaction of either electron-rich or –deficient phenols with trichloroethylene to give the resultant dichlorovinyl ethers in high yields. Site selective palladium-catalyzed cross-coupling for the specific functionalization of a single C-Cl bond was developed, and could install alkyl, alkenyl, alkynyl and (hetero)aryl moieties. The resulting electrophiles could be reacted with a second organometallic nucleophile forming trisubstituted, electron-rich alkenes, dienes, trienes or enynes in only two or three steps. Alternatively, the product from the first cross-coupling reaction could be isolated, deprotonated and quenched with an electrophile, then cross-coupled with a second organometallic nucleophile to give tetrasubstituted, electron-rich alkenes and dienes. In the course of studying the site selective cross-coupling, it was found that prolonged exposure of the C1-functionalized materials to palladium promoted an intramolecular C-H activation, forming 2-substituted benzofurans. This reaction proved to be very general, and a wide variety of benzofurans were synthesized, containing both electron-withdrawing and electron-donating group groups in the donor arenes, as well as alkyl, alkenyl, alkynyl and aryl functionalities at the 2-position. This method was also extended to the synthesis of 2-substituted indoles from anilines, trichloroethylene and boronic acids. en
dc.format.extent 12707402 bytes
dc.format.mimetype application/pdf
dc.language.iso en_US
dc.rights info:eu-repo/semantics/openAccess
dc.subject palladium en
dc.subject heterocycles en
dc.subject direct arylation en
dc.subject cross-coupling en
dc.subject boronic acids en
dc.subject trichloroethylene en
dc.title A diversity-oriented approach to the palladium-catalyzed modular assembly of conjugated compounds and heterocycles: high-value compounds from trichloroethylene en
dc.type info:eu-repo/semantics/doctoralThesis
dc.degree.discipline Chemistry en
dc.contributor.examiningcommittee Budzelaar, Peter H. M. (Chemistry) Sorensen, John L. (Chemistry) Hasinoff, Brian B. (Pharmacy) Lautens, Mark (Chemistry, University of Toronto) en
dc.degree.level Doctor of Philosophy (Ph.D.) en
dc.description.note February 2011 en

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