Electroreductive Cyclization Reactions 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 project dealing with the use of electrochemical techniques                 in organic synthesis is being supported by the Organic and                      Macromolecular Chemistry Program.  Linear molecules containing                  two or more distal functional groups are being subjected to                     electrolysis to generate a radical anion at one site which will                 react by carbon-carbon bond formation at the other functional                   group resulting in the formation of ring-containing compounds.                  This research is centered on an attempt to understand the                       various factors which govern the cyclization process.                                                                                                           Electroreductive cyclization reactions are being studied in                     detail with a special emphasis placed upon an examination of                    the following items:  A. 1.  Can substituents positioned at                     "strategically important locations" on the tether be used as                    stereocontrol elements allowing for the regulation of both                      relative and absolute stereochemistry?  2.  Can proton donor                    surrogates (e.g., Me3SiCl) and/or captodative effects be used                   to facilitate cyclization at the expense of the unwanted C-C pi                 bond hydrogenation which occasionally accompanies                               electroreductive cyclizations involving ketones?  3.  Can                       electroreductive cyclizations be conducted using a substrate                    wherein the alpha, beta-unsaturated ester unit is tethered to                   an ester (a lactone), an acid anhydride, or an acid halide?  4.                 Can the results of these investigations be used to design and                   implement a rational synthesis of the biologically important                    and architecturally interesting phorbol esters?  B.  Can                        mediators such as vitamin B12 or cobaloxime be used in                          electroreductive cyclization reactions and, if so, can the                      reactions be conducted catalytically?  The results of these                     studies are being applied to model studies directed toward                      construction of bicycloı5.3.O!undecane framework common to a                    host of natural products.  C.  Finally, the synthetic utility                   of electroreductive cyclization reactions involving systems                     containing the carbon-carbon triple bond (e.g., alkynones and                   alkynoates) linked to an easily reduced alkylidene malonate or                  an alkylidene Meldrum's acid subunit is being examined.  In                     this way, the initially formed alpha, beta-unsaturated carbonyl                 compound should be inert to the conditions under which the                      reduction is conducted and will consequently be available for                   further elaboration.  Additional studies focusing upon the use                  of a cyclopropyl Meldrum's acid subunit (a spiroacylal) are                     being carried out.
[{'FirstName': 'Manuel', 'LastName': 'Baizer', 'PI_MID_INIT': None, 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Manuel Baizer', 'EmailAddress': None, 'NSF_ID': '000212853', 'StartDate': '05/01/1988', 'EndDate': None, 'RoleCode': 'Co-Principal Investigator'}, {'FirstName': 'R. Daniel', 'LastName': 'Little', 'PI_MID_INIT': None, 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'R. Daniel Little', 'EmailAddress': 'little@chem.ucsb.edu', 'NSF_ID': '000333647', 'StartDate': '05/01/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}]
{'Name': 'University of California-Santa Barbara', 'CityName': 'SANTA BARBARA', 'ZipCode': '931060001', 'PhoneNumber': '8058934188', 'StreetAddress': '3227 CHEADLE HALL', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'California', 'StateCode': 'CA', 'CONGRESSDISTRICT': '24', 'CONGRESS_DISTRICT_ORG': 'CA24', 'ORG_UEI_NUM': 'G9QBQDH39DF4', 'ORG_LGL_BUS_NAME': 'UNIVERSITY OF CALIFORNIA, SANTA BARBARA', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '195000', 'Text': 'METHODOLOGY'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8719617.xml'}