Copper-Promoted Oxidation and Oxygenation Reactions of      Nitrogen-Containing Aliphatic Compounds (Chemistry)
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Benjamin F. Plummer'}
This grant in the Organic and Macromolecular Chemistry Program                  supports research of Professors Lawrence Sayre and Fred Urbach,                 which aims at a mechanistic study concerning the role of copper                 as a catalyst in the oxidation of organic compounds.  Such                      processes have far reaching consequences in both biochemical                    and industrial processes.  The use of more simplified model                     systems to study these multifaceted processes that involve                      different oxidation states of copper at specific places in the                  catalytic cycle provides considerable insight into how nature                   achieves such chemical reactions.                                                                                                                               The planned research is divided into four sections.  The first                  examines the dehydrogenation of unactivated amines and the                      oxidative cleavage of beta-hetero-atom-substituted amines.  The                 second involves a model study for the copper amine oxidases in                  which a quinone-mediated transamination is followed by                          copper-mediated  oxidation of the resulting aminophenol.  The                   third aspect deals with oxidations of amino acids and simple                    N-acyl derivatives thereof.  The fourth examines the                            regioselective copper-mediated oxidative N-dealkylation of                      oligopeptides at the C-terminus as possible mechanisms for the                  copper amidases which convert peptidylglycine to peptide                        carboxamides.  Initial studies in these areas make it clear                     that multiple reaction pathways are possible in many cases.                     The planned work involves a deeper and more quantitative                        characterization of the reaction in terms of (1) the factors                    which control competitive reaction pathways, (2) substrate                      structure-reactivity effects, (3) the effect of varying the                     oxidation system ?e.g., Cu(I)-dioxygen vs.                                      Cu(II)-peroxydisulfate vs. Cu(III)!, and (4) the effect of the                  metal coordination environment and other reaction conditions.
[{'FirstName': 'Fred', 'LastName': 'Urbach', 'EmailAddress': None, 'StartDate': '07/15/1987', 'EndDate': None, 'RoleCode': 'Co-Principal Investigator'}, {'FirstName': 'Lawrence', 'LastName': 'Sayre', 'EmailAddress': 'lms3@po.cwru.edu', 'StartDate': '07/15/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}]
{'Name': 'Case Western Reserve University', 'CityName': 'CLEVELAND', 'ZipCode': '441064901', 'PhoneNumber': '2163684510', 'StreetAddress': 'Nord Hall, Suite 615', 'CountryName': 'United States', 'StateName': 'Ohio', 'StateCode': 'OH'}
[{'Code': '1938', 'Text': 'Chemical Instrumentation'}, {'Code': '1944', 'Text': 'BIMOLECULAR PROCESSES'}]
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8706263.xml'}