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I. Reactions of Bicyclo[3.3.0]octenyl Tosylates II. Nitrogen-15 Nuclear Magnetic Resonance Investigations of Organic Reactions

Citation

Nee, Michael Wei-Kuo (1982) I. Reactions of Bicyclo[3.3.0]octenyl Tosylates II. Nitrogen-15 Nuclear Magnetic Resonance Investigations of Organic Reactions. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/82re-5t35. https://resolver.caltech.edu/CaltechTHESIS:05162018-111927806

Abstract

PART I

A. Elimination Reactions of 6-Bicyclo[3.2.0]-2-heptenyl Tosylates

The 6- and 7-bicyclo[3.3.0]-2-octenyl tosylates with 2,4,6-trimethylpyridine have been reported to yield mixtures of bicyclo[3.3.0]octa-2,6-diene and bicyclo[3.3.0]octa-2,7-diene. Under the same conditions, the stereoisomeric 6-bicyclo[3.2.0]-2-heptenyl tosylate gives ring-opened products, 1,3,5-cycloheptatriene and 5-ethylidene-1,3-cyclopentadiene.

B. Acetolysis of Some Bicyclo[3.3.0]-2-octenyl Tosylates

The products of the acetolysis of the stereoisomeric 6-,7-, and 8-bicyclo[3.3.0]-2-octenyl tosylates are reported. These tosylates were themselves stable to skeletal rearrangements, but were found to undergo 1,2-hydride shifts and elimination solvolysis.

PART II

Assignment of the Nitrogen-15 Nuclear Magnetic Resonances of Biotin and Unequivocal Synthesis of (+)-[1-15N]Biotin

The 15N NMR spectra of biotin, desthiobiotin, and 2-imidazolidinone were measured. Assignment of the resonances of biotin and desthiobiotin was achieved by off-resonance decoupling. The biotin assignment was confirmed by measurement of biotin specifically labeled with 15N at N1.

PART III

A 15N Nuclear Magnetic Resonance Study of the Base-Catalyzed -NH2 Exchange Reactions of Acetamide and Thioacetamide

The base-catalyzed -NH2 exchange reactions of acetamide and thioacetamide were studied by 15N nuclear magnetic resonance spectroscopy by use of line-shape analysis. The 15N NMR spectra of these primary amides at intermediate exchange rates were broad doublets, which indicated that the two amide protons were exchanging at different rates. The line-shape analysis indicated that the ratio of exchange rates was 6 ± 1 for acetamide and 3 ± 1 for thioacetamide.

PART IV

Determination of the Binding Interactions of cis-[Pt(NH3)2Cl2] with Nucleosides by 15N Nuclear Magnetic Resonance Spectroscopy

The 15N NMR chemical shifts and 15N-195Pt coupling constants of several platinum(II)-ammine complexes were measured. The magnitude of the coupling constants were dependent on the trans ligand. A similar dependence on the trans ligand was found for the 15N chemical shifts of the coordinated ammonia ligands. The magnitude of the 15N platinum coordination shift was proportional to the 15N protonation shift of the ligand. Cis-[Pt(NH3)2Cl2] was found to bind to guanosine through N7 and another nitrogen site. The drug also binds to N3 of cytidine and to all four of the nitrogen sites of adenosine. No evidence was found to support chelate binding of nucleosides by cis-[Pt(NH3)2Cl2].

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry; Biology
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Minor Option:Biology
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Ireland, Robert E.
Thesis Committee:
  • Roberts, John D. (chair)
  • Ireland, Robert E.
  • Richards, John H.
  • Grubbs, Robert H.
Defense Date:16 October 1981
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
NSFGM-11072
Record Number:CaltechTHESIS:05162018-111927806
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:05162018-111927806
DOI:10.7907/82re-5t35
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jo00318a037DOIArticle adapted for Part IA.
https://doi.org/10.1021/jo00314a014DOIArticle adapted for Part IB.
https://doi.org/10.1021/ja00406a054DOIArticle adapted for Part II.
https://doi.org/10.1002/mrc.1270180302DOIArticle adapted for Part III.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10898
Collection:CaltechTHESIS
Deposited By: Melissa Ray
Deposited On:02 Jul 2018 23:36
Last Modified:16 Apr 2021 22:24

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