Enantioselective Organic Syntheses  (Chemistry)
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'John S. Showell', 'PO_EMAI': None, 'PO_PHON': None}
The continuing challenge in the area of organic synthesis is to                 develop synthetic reactions that have generality, yet exhibit                   great selectivity.  Dr. Molander has discovered a way to take                   an old reaction, the so-called Reformatsky reaction, and                        greatly increase its usefulness in the synthesis of complex                     natural products like the beta-lactam antibiotics.  This                        project is in the Organic and Macromolecular Chemistry Program.                                                                                                 This will develop novel entries into complex, enantiomerically                  pure organic substrates.  The first aspect of the research will                 explore use of samarium diiodide-induced intramolecular                         Reformatsky reactions.  Full development of this methodology                    will permit access to syn 1,3-diols by 1,3-asymmetric induction                 in a carbon-carbon bond-forming process.  Facile generation of                  HMG-CoA reductase inhibitors is one of many important                           contributions that this advancement will permit.  Application                   to nitrogen-containing substrates is also planned, and                          important new routes to pharmacologically important                             aminoglycoside and beta-lactam antibiotics will result from                     this aspect of the study.                                                                                                                                       Chemistry based upon samarium diiodide reduction of vinyl                       oxiranes comprises the second aspect of the study.  Allylic                     alcohols generated by this process will be incorporated into                    several natural products syntheses, including leukotriene B4.                   Another unique method for 1,3-asymmetric induction is planned,                  involving intramolecular Michael addition of samarium-based                     Reformatsky reagents to conjugated olefins.  A novel                            cyclopropanation reagent, Sm/CH2I2, will be thoroughly studied                  to determine its unique role in organic synthesis, utilizing                    allylic alcohols as substrates in the first aspect of studies                   in this area.                                                                                                                                                   Stereocontrolled cyclizations onto chiral epoxides constitute                   another proposed approach to chiral carbocycles and                             heterocyclic substrates.  Reactions utilizing alkynylborates                    and allylsilanes will be explored to provide access to organic                  molecules in which up to three contiguous stereocenters are                     controlled in a completely predictable fashion.                                                                                                                 Finally, the chemistry of epoxy anions will be explored.  These                 unique nucleophiles may very well revolutionize the manner in                   which the versatile epoxide functional group is incorporated                    into organic molecules.
{'FirstName': 'Gary', 'LastName': 'Molander', 'PI_MID_INIT': 'A', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Gary A Molander', 'EmailAddress': 'gmolandr@sas.upenn.edu', 'NSF_ID': '000392380', 'StartDate': '07/01/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of Colorado at Boulder', 'CityName': 'Boulder', 'ZipCode': '803090001', 'PhoneNumber': '3034926221', 'StreetAddress': '3100 MARINE ST', 'StreetAddress2': 'STE 481 572 UCB', 'CountryName': 'United States', 'StateName': 'Colorado', 'StateCode': 'CO', 'CONGRESSDISTRICT': '02', 'CONGRESS_DISTRICT_ORG': 'CO02', 'ORG_UEI_NUM': 'SPVKK1RC2MZ3', 'ORG_LGL_BUS_NAME': 'THE REGENTS OF THE UNIVERSITY OF COLORADO', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '1948', 'Text': 'SYNTHESIS'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8704178.xml'}