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dc.contributor.authorMorrison, Matthewen
dc.date2009-09-29 13:58:35.186
dc.date.accessioned2009-10-07T15:49:42Z
dc.date.available2009-10-07T15:49:42Z
dc.date.issued2009-10-07T15:49:42Z
dc.identifier.urihttp://hdl.handle.net/1974/5265
dc.descriptionThesis (Master, Chemistry) -- Queen's University, 2009-09-29 13:58:35.186en
dc.description.abstractThis thesis details a straightforward synthetic route to the antifungal compound pyrrolnitrin 1.2, along with several analogous halogenated phenylpyrroles. The proposed synthetic protocol involved the Suzuki-Miyaura cross-coupling of appropriately halogenated pyrrole pinacolboronate esters and aryl compounds. In the efforts towards preparing the cross-coupling partners, we report a regiospecific and high yielding synthesis of a 3-chloro pyrrole compound 2.14, its brominated analog 2.16, an iodinated analog 2.17, and the corresponding pinacolboronate ester 2.18. We also report a generalized reaction sequence (lithiation/carboxylation/Schmidt reaction/oxidation) for the preparation of halogenated benzoic acids, anilines and nitrobenzenes. In particular, we synthesized the desired halogenated nitrobenzene coupling partner 3.27 in excellent yield. We were also able to show that the conditions employed in this sequence were mild enough to allow preparation of the 2-bromo-6-iodo compound 3.33. Once the coupling partners were prepared, we developed the optimal conditions for our Suzuki-Miyaura cross-coupling reactions. In doing so, we were able to prepare our target compound 1.2 and several halogenated analogs in good yields. We also prepared brominated and deuterated arylpyrroles 4.27 and 4.28, respectively, for future use in mechanistic studies of the pyrrolnitrin biosynthetic enzymes, PrnB, Prn C and PrnD. This required preparation of the corresponding brominated and deuterated pyrrole pinacolboronate esters 4.24 and 4.26.en
dc.format.extent5792280 bytes
dc.format.mimetypeapplication/pdf
dc.language.isoengen
dc.relation.ispartofseriesCanadian thesesen
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectpyrrolnitrin, halogenases, Schmidt reaction, Directed ortho Metalation, 2,6-dihaloanilines, 2,6-dihalonitrobenzenes, 3-substituted pyrroles, cross-coupling with pyrrolesen
dc.titleA Convenient Synthesis of Pyrrolnitrin and Related Halogenated Phenylpyrrolesen
dc.typethesisen
dc.description.degreeM.Sc.en
dc.contributor.supervisorPratt, Derek A.en
dc.contributor.departmentChemistryen
dc.degree.grantorQueen's University at Kingstonen


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