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dc.contributor.advisorDaniel S. Kemp.en_US
dc.contributor.authorJob, Gabriel Ethanen_US
dc.contributor.otherMassachusetts Institute of Technology. Dept. of Chemistry.en_US
dc.date.accessioned2006-03-29T18:48:28Z
dc.date.available2006-03-29T18:48:28Z
dc.date.copyright2005en_US
dc.date.issued2005en_US
dc.identifier.urihttp://hdl.handle.net/1721.1/32481
dc.descriptionThesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005.en_US
dc.descriptionVita.en_US
dc.descriptionIncludes bibliographical references.en_US
dc.description.abstractI. An improved Ullmann reaction for N- or O-arylation of 1,2-aminoalcohols with aryl iodides is described. The procedures enjoy several advantages over traditional methods: a substoichiometric amount of copper catalyst is employed, the reactions take place in low boiling and non-toxic solvents such as isopropanol, the reactions occur at relatively low temperatures, and a variety of non-activated aryl iodide substrates may be used. II. Recent advances in solubilization of polyalanine and helix stabilization by end capping were combined to synthesize a series of highly helical, water-soluble polyalanine peptides permitting straightforward context-free investigation of this most common helix- forming [alpha]-amino acid. Three types of peptides incorporating this helical polyalanine region were made, each for a specific purpose: structure determination by NMR; fractional helicity measurement by amide NH to ND exchange in D₂0, observed by NMR; and CD analysis. CD spectra of these helical peptides were used to directly verify an equation used for peptide structural analysis. The helix-initiating N-terminal cap (Hel) used to create the highly helical polyalanines is a synthetically modified Pro-Pro dipeptide. Hel was developed in the Kemp group a decade ago, and peptides created with it have been extensively studied in this group. However, the 18-step synthesis of Hel has hindered its use by others. Therefore, simpler analogs of Hel have been made and preliminary studies have been conducted. The simpler N-caps were synthesized in twelve steps or fewer and proved effective at helix initiation, as judged by CD spectroscopy.en_US
dc.description.abstract(cont.) The studies reported herein have also identified an even simpler helix initiator: the dipeptide sequence .... Further evaluation of these new N-caps under conditions that are not ideal for helix formation awaits.en_US
dc.description.statementofresponsibilityby Gabriel E. Joben_US
dc.format.extent225 p.en_US
dc.format.extent12070337 bytes
dc.format.extent12084600 bytes
dc.format.mimetypeapplication/pdf
dc.format.mimetypeapplication/pdf
dc.language.isoengen_US
dc.publisherMassachusetts Institute of Technologyen_US
dc.rightsM.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.en_US
dc.rights.urihttp://dspace.mit.edu/handle/1721.1/7582
dc.subjectChemistry.en_US
dc.titleCopper-catalyzed arylation of 1,2-amino alcohols. Synthesis of N-terminal, peptide helix initiators, and characterization of highly helical, capped polyalanine peptidesen_US
dc.typeThesisen_US
dc.description.degreePh.D.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry
dc.identifier.oclc61773210en_US


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