C-C Bond Formation via Alkyl Cobaloxime Radical Chemistry:  New Synthetic Reactions and Bio-Organic Applications
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'George M. Rubottom', 'PO_EMAI': None, 'PO_PHON': None}
The Organic and Macromolecular Program is supporting research                   directed toward the study of organometallic reagents related to                 vitamin B12.  A series of novel chemical reactions have been                    discovered in which organo-cobalt (III) reagents mediate the                    cross coupling of varied structure types which leads to the                     construction of several biologically important compounds.                                                                                                       Three different types of novel radical cross coupling reactions                 mediated via alkyl cobaloximes ıR-CoIII(dmgH)2py; dmgH =                        dimethylglyoxime monoanion! are being studied:  (1)                             alkyl-alkenyl cross coupling, (2) alkyl-protonated                              heteroaromatic cross coupling, and (3) alkyl-nitroalkylanion                    cross coupling.  A unique feature of these radical-mediated                     reactions, compared to other synthetically important radical                    reactions, is regeneration of the original olefin, protonated                   heteroaromatic, or nitroalkylanion functionality in the                         product.                                                                                                                                                        This research will continue the study of cobaloxime-mediated                    cross couplings and applications to (1) the development of a                    radical equivalent to the Grignard reaction, compatible with                    hydroxylic solvents and most of the common organic functional                   groups, via stoichiometric alkyl-nitroakylanion cross coupling,                 (2) a synthesis of the nucleoside antibiotic tunicamycin V and                  the development of a general strategy for the preparation of                    tunicamycins and analogs via stoichiometric                                     alkyl-nitroalkylanion cross couplings,  (3) a general strategy                  for the synthesis of C-di-, C-oligo-, and C-polysaccharides,                    essentially unexplored classes of bio-organically interesting                   and potentially significant unnatural analogs of natural                        products, via alkyl-nitroalkylanion cross coupling of valuable                  monosaccharides, and (4) preparation of two new classes of                      penicillin analogs, designed to be mechanism-based inhibitors                   of bacterial beta-lactamase self-defense enzymes, via                           alkyl-alkenyl or alkyl-protonated heteroaromatic cross                          couplings.
{'FirstName': 'Bruce', 'LastName': 'Branchaud', 'PI_MID_INIT': 'P', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Bruce P Branchaud', 'EmailAddress': 'bbranch@oregon.uoregon.edu', 'NSF_ID': '000093375', 'StartDate': '07/01/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of Oregon Eugene', 'CityName': 'EUGENE', 'ZipCode': '974031905', 'PhoneNumber': '5413465131', 'StreetAddress': '1776 E 13TH AVE', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Oregon', 'StateCode': 'OR', 'CONGRESSDISTRICT': '04', 'CONGRESS_DISTRICT_ORG': 'OR04', 'ORG_UEI_NUM': 'Z3FGN9MF92U2', 'ORG_LGL_BUS_NAME': 'UNIVERSITY OF OREGON', 'ORG_PRNT_UEI_NUM': 'Z3FGN9MF92U2'}
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{'Code': '1950', 'Text': 'METHODOLOGY'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1988&All=true', 'xml': '8806805.xml'}