Heteroallyl and alpha-Heterosubstituted Allyllithium        Reagents
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Thomas C. Farrar', 'PO_EMAI': None, 'PO_PHON': None}
This grant in Organic and Macromolecular Chemistry provides                     support for Dr. Lloyd Jackman, Pennsylvania Stata University.                   The work focuses on the chemistry and mechanisms of various                     organic salts, particularly those involving lithium. These                      species are among the most important reagents used in synthetic                 chemistry and an understanding of their fundamental aspects has                 important practical significance.                                                                                                                               The most important single group of synthetically useful organic                 reactions is that based on ambident anions of the type                          C=C-X(-). The number of representatives of this group is                        rapidly increasing.  A proper mechanistic understanding of the                  reactions of these anions with electrophiles does not exist, in                 part because the structures of the ambident anion salts in                      solution are usually unknown.  With methodologies for solving                   such structural problems in the case of lithium salts, this                     study will extend our knowledge by effecting a comparison                       between the 13C, 6Li, and 7Li nmr spectral characteristics in                   solution with those in the solid state for known crystal                        structures.  All the above techniques will be applied to                        lithium enolates, ester enolates and enamides and to                            heterosubstituted allyllithium reagents.  It is becoming clear                  that mixed aggregates (dimers, tetramers) between lithium                       carbanion salts and lithium salts which are strong electrolytes                 are important entities in weakly polar solvents in that they                    control rates and regiochemistry.  The thermodynamics of mixed                  aggregate formation will be studied in order to determine the                   factors controlling their stabilities.  The structural                          information will be used in conjunction with reaction kinetics                  to establish the reaction mechanisms of the transesterification                 of lithium phenolates, the aldol reaction, and the alkylation                   of phenolates, enolates, and enamides.  Particular emphasis                     will be placed on defining the primary reactant species and                     understanding the role of mixed aggregates as intermediate                      species.  The involvement of coordination induced proximity                     effects arising when the electrophilic reagents possess basic                   centers which can interact with lithium in aggregates will also                 be probed.  The reactions to be studied include some that are                   widely used in synthetic organic chemistry.  The results of                     these studies should allow synthetic chemists to perform them                   more efficiently and to design new ones for achieving high                      regio- and stereo-selectivities.
{'FirstName': 'Lloyd', 'LastName': 'Jackman', 'PI_MID_INIT': 'M', 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Lloyd M Jackman', 'EmailAddress': None, 'NSF_ID': '000388412', 'StartDate': '06/01/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'Pennsylvania State Univ University Park', 'CityName': 'UNIVERSITY PARK', 'ZipCode': '168021503', 'PhoneNumber': '8148651372', 'StreetAddress': '201 OLD MAIN', 'StreetAddress2': None, 'CountryName': 'United States', 'StateName': 'Pennsylvania', 'StateCode': 'PA', 'CONGRESSDISTRICT': '15', 'CONGRESS_DISTRICT_ORG': 'PA15', 'ORG_UEI_NUM': 'NPM2J7MSCF61', 'ORG_LGL_BUS_NAME': 'THE PENNSYLVANIA STATE UNIVERSITY', 'ORG_PRNT_UEI_NUM': None}
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{'Code': '1944', 'Text': 'BIMOLECULAR PROCESSES'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1988&All=true', 'xml': '8801884.xml'}