Persistent Link:
http://hdl.handle.net/10150/185270
Title:
NMR studies of dimeric and polymeric lactams.
Author:
Micheli, Bernard Jean Marie.
Issue Date:
1990
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
The aim of this work was to study the solution conformation of dimeric and polymeric 1actams. In a first part of this work, the synthesis of bicyc1odi1actams as precursors of the polymers was explored. A new preparation for the 2, 5-diazabicyc1o [2,2,2] octa-3, 6-dione was developed. The dimers and polymers were obtained from the N-protected cis- and trans- 3-amino-6-carboxy-2-piperidone for which an improved synthesis was found. Base treatment of the trans activated ester led to the polymer. Using the methods of solution phase peptide synthesis, the four possible dimers were prepared. After transformation to the paranitrophenyl esters, they polymerized to oligomeric species under the same treatment. The solution conformation of the monomeric, dimeric and polymeric species was determined by 1- and 2-dimensional NMR techniques. The 1actam rings have a chair-like conformation in solution. The cis- 1actam is a powerful β-turn- inducer when incorporated in synthetic peptides. The cis- lactam was found, however, to have a very similar conformation in DMSO solution, without hydrogen bonding to stabilize the turn. No evidence was found for the β-turn in the dimers and polymers using 2-dimensional NMR techniques. The dimers were found to exist in an extended conformation in DMSO. The fact that every other amide bond is in the cis configuration, as well as the steric crowding due to the rings may not allow the existence of the β-turn.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Chemistry.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Hall, Henry K., Jr.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleNMR studies of dimeric and polymeric lactams.en_US
dc.creatorMicheli, Bernard Jean Marie.en_US
dc.contributor.authorMicheli, Bernard Jean Marie.en_US
dc.date.issued1990en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThe aim of this work was to study the solution conformation of dimeric and polymeric 1actams. In a first part of this work, the synthesis of bicyc1odi1actams as precursors of the polymers was explored. A new preparation for the 2, 5-diazabicyc1o [2,2,2] octa-3, 6-dione was developed. The dimers and polymers were obtained from the N-protected cis- and trans- 3-amino-6-carboxy-2-piperidone for which an improved synthesis was found. Base treatment of the trans activated ester led to the polymer. Using the methods of solution phase peptide synthesis, the four possible dimers were prepared. After transformation to the paranitrophenyl esters, they polymerized to oligomeric species under the same treatment. The solution conformation of the monomeric, dimeric and polymeric species was determined by 1- and 2-dimensional NMR techniques. The 1actam rings have a chair-like conformation in solution. The cis- 1actam is a powerful β-turn- inducer when incorporated in synthetic peptides. The cis- lactam was found, however, to have a very similar conformation in DMSO solution, without hydrogen bonding to stabilize the turn. No evidence was found for the β-turn in the dimers and polymers using 2-dimensional NMR techniques. The dimers were found to exist in an extended conformation in DMSO. The fact that every other amide bond is in the cis configuration, as well as the steric crowding due to the rings may not allow the existence of the β-turn.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectChemistry.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorHall, Henry K., Jr.en_US
dc.contributor.committeememberBates, Robert B.en_US
dc.contributor.committeememberPolt, Robin L.en_US
dc.contributor.committeememberBarfield, Michaelen_US
dc.contributor.committeememberSalzman, Williamen_US
dc.identifier.proquest9111955en_US
dc.identifier.oclc710824036en_US
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