Studies in Organosulfur Chemistry
{'Code': '03090003', 'Directorate': {'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'John S. Showell'}
This research will lead to new methods of synthesizing complex                  molecules.  It is being funded by the Organic and                               Macromolecular Chemistry Program.  This work will permit the                    investigation of an unusual new class of molecules that contain                 the cyclic sulfur analog of cyclic peroxides.  It has the                       potential to produce molecules with unusual chemical and                        biological properties.                                                                                                                                          Four-membered rings with two adjacent sulfur atoms, known as                    1,2-dithietanes, are of fundamental theoretical, chemical and                   biological interest.  Although postulated as transient                          intermediates, no representative of this class of compounds was                 known as a stable compound until the recent disclosure of the                   first stable compound in this series, 1,2-dithiatopazine.  The                  chemistry and biology of this compound will be investigated.  A                 series of other 1,2 dithietanes will also be targeted for                       synthesis and those compounds proven stable will also be                        studied.  The targeted systems were designed to probe the                       effect of molecular framework flanking the 1,2-dithietane                       moiety including the size of the adjacent rings and the                         presence of nitrogen and carbon in them. Molecular mechanics                    calculations will also be performed in attempts to predict the                  stability of designed systems.                                                                                                                                  Several alternative methods for the synthesis of thionolactones                 will be explored.  The chemistry of these intermediates will be                 studied with particular emphasis on new C-C bond forming                        reactions and cyclic ether formation.  Thus, the intermolecular                 coupling of dithionolactones using electron transfer processes                  and subsequent chemistry will also be followed as a route to                    complex polycyclic systems.  Dithionoesters will also be                        synthesized and their intramolecular coupling will be                           investigated as a means to construct cyclic frameworks.                                                                                                         The reasons for the special stability of 1,2-dithiatopazine are                 not quite clear at present.  Calculations on the stability of                   the systems are expected to lead to intesting predictions which                 will be tested experimentally.  Also theoretical predictions                    regarding the physical, chemical and biological properties of                   these molecules are intriguing and will be put to the test.                     Furthermore, the power and scope to the projected methodology                   for the formation of the 1,2-dithietanes involving C-C bond                     formation could be important in ring construction.  These                       fundamental reactions and other extensions involving the                        thionocarbonyl functionality will be investigated and have the                  potential of becoming useful synthetic methods.
{'FirstName': 'Kyriacos C.', 'LastName': 'Nicolaou', 'EmailAddress': 'kcn@scripps.edu', 'StartDate': '02/01/1988', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
{'Name': 'University of Pennsylvania', 'CityName': 'Philadelphia', 'ZipCode': '191046205', 'PhoneNumber': '2158987293', 'StreetAddress': 'Research Services', 'CountryName': 'United States', 'StateName': 'Pennsylvania', 'StateCode': 'PA'}
{'Code': '1948', 'Text': 'SYNTHESIS'}
{'url': 'https://www.nsf.gov/awardsearch/download?DownloadFileName=1987&All=true', 'xml': '8718024.xml'}