Investigation of Transannular Free-Radical Cyclizations in  Organic Synthesis (Chemistry)
{'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}
This program is being supported by the Organic and                           Macromolecular Chemistry Program. The project involves the                      construction of a series of naturally occurring compounds of                    unusual structure. The synthetic strategy into these compounds                  involves a novel approach in that a large ring structure will                   be transformed in a single step to structures which contain two                 or more rings of smaller size.                                                      The goal is to demonstrate the viability of a powerful and                  little-studied carbon-carbon bond forming reaction,                             transannular free-radical cyclization, in the context of a                      complex synthetic problem. The method is to be illustrated                      through the synthesis of the cembranoid natural product,                        7,8-epoxy-4-basmen-6-one, which features as the key step two                    sequential transannular cyclization reactions in a                              fourteen-membered macrocyclic precursor. This synthetic                         strategy will allow certain structural and stereochemical                       features of the macrocyclic ring to be employed in a highly                     specific fashion during the transannular ring-closures.                         Molecular mechanics calculations will be employed along with                    X-ray crystallographic to predict preferred transition state                    geometries of the reactants and relevant reactive                               intermediates. High field NMR spectroscopy will be used to                      determine conformations in solution as an adjunct to the tools                  noted above.
{'FirstName': 'Andrew', 'LastName': 'Myers', 'PI_MID_INIT': 'G', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Andrew G Myers', 'EmailAddress': 'myers@chemistry.harvard.edu', 'NSF_ID': '000234799', 'StartDate': '12/01/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'California Institute of Technology', 'CityName': 'PASADENA', 'ZipCode': '911250001', 'PhoneNumber': '6263956219', 'StreetAddress': '1200 E CALIFORNIA BLVD', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'California', 'StateCode': 'CA', 'CONGRESSDISTRICT': '28', 'CONGRESS_DISTRICT_ORG': 'CA28', 'ORG_UEI_NUM': 'U2JMKHNS5TG4', 'ORG_LGL_BUS_NAME': 'CALIFORNIA INSTITUTE OF TECHNOLOGY', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '1950', 'Text': 'METHODOLOGY'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8715337.xml'}