{"@context":"http://iiif.io/api/presentation/2/context.json","@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/manifest.json","@type":"sc:Manifest","label":"The Synthesis of Polycyclic Fused-Ring Systems via Rh(I)-Catalyzed Higher Order Cycloaddition Reactions with Carbon Monoxide","metadata":[{"label":"dc.description.sponsorship","value":"This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree."},{"label":"dc.format","value":"Monograph"},{"label":"dc.format.medium","value":"Electronic Resource"},{"label":"dc.identifier.uri","value":"http://hdl.handle.net/11401/77084"},{"label":"dc.language.iso","value":"en_US"},{"label":"dc.publisher","value":"The Graduate School, Stony Brook University: Stony Brook, NY."},{"label":"dcterms.abstract","value":"Abstract of the Dissertation The Synthesis of Polycyclic Fused-Ring Systems via Rh(I)-Catalyzed Higher Order Cycloaddition Reactions with Carbon Monoxide by Alexandra A. Athan Doctor of Philosophy in Chemistry Stony Brook University 2013 The seven-membered ring is a common motif in various bioactive natural products. Many examples of natural product cores possessing fused-ring systems are also prevalent. Therefore, it is useful to provide methods that allow access to these cores rapidly and efficiently. We have previously reported the successful construction of fused-ring skeletons containing seven-membered rings via Rh-catalyzed carbocyclization and cycloaddition reactions. As part of our continuing study on higher order metal-catalyzed reactions, novel dienynes, enediynes and triynes have been subjected to the Rh-catalyzed [2+2+2+1] cycloaddition reaction. In the presence of Rh under CO, cycloheptene-diynes were converted to the corresponding 5-7-7-5 tetracyclic products. Variable amounts of [2+2+2] byproducts were also observed. We would like to further extend this methodology to synthesize new classes of colchicine and allocolchicine derivatives. Novel triyne substrates have been synthesized and subjected to our previously developed Rh(I)-catalyzed cycloaddition reactions. The 6-7-6-7 tetracyclics have been obtained in good yields in the presence of [Rh(cod)Cl2]2  and DPPP in TFE using microwave irradiation. The 6-7-7-6 carbonylated tetracyclics have also been obtained under ambient CO pressures in toluene. The scope and the mechanism of these novel processes will be discussed."},{"label":"dcterms.available","value":"2017-09-20T16:51:55Z"},{"label":"dcterms.contributor","value":"Rojas, Christian."},{"label":"dcterms.creator","value":"Athan, Alexandra"},{"label":"dcterms.dateAccepted","value":"2017-09-20T16:51:55Z"},{"label":"dcterms.dateSubmitted","value":"2017-09-20T16:51:55Z"},{"label":"dcterms.description","value":"Department of Chemistry."},{"label":"dcterms.extent","value":"196 pg."},{"label":"dcterms.format","value":"Monograph"},{"label":"dcterms.identifier","value":"http://hdl.handle.net/11401/77084"},{"label":"dcterms.issued","value":"2013-12-01"},{"label":"dcterms.language","value":"en_US"},{"label":"dcterms.provenance","value":"Made available in DSpace on 2017-09-20T16:51:55Z (GMT). No. of bitstreams: 1\nAthan_grad.sunysb_0771E_11502.pdf: 7771481 bytes, checksum: 15dd0e1248338f6b8d582f562179dfbe (MD5)\n  Previous issue date:    1"},{"label":"dcterms.publisher","value":"The Graduate School, Stony Brook University: Stony Brook, NY."},{"label":"dcterms.subject","value":"Chemistry"},{"label":"dcterms.title","value":"The Synthesis of Polycyclic Fused-Ring Systems via Rh(I)-Catalyzed Higher Order Cycloaddition Reactions with Carbon Monoxide"},{"label":"dcterms.type","value":"Dissertation"},{"label":"dc.type","value":"Dissertation"}],"description":"This manifest was generated dynamically","viewingDirection":"left-to-right","sequences":[{"@type":"sc:Sequence","canvases":[{"@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/canvas/page-1.json","@type":"sc:Canvas","label":"Page 1","height":1650,"width":1275,"images":[{"@type":"oa:Annotation","motivation":"sc:painting","resource":{"@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/90%2F29%2F15%2F90291581556331733804866111203650212854/full/full/0/default.jpg","@type":"dctypes:Image","format":"image/jpeg","height":1650,"width":1275,"service":{"@context":"http://iiif.io/api/image/2/context.json","@id":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/90%2F29%2F15%2F90291581556331733804866111203650212854","profile":"http://iiif.io/api/image/2/level2.json"}},"on":"https://repo.library.stonybrook.edu/cantaloupe/iiif/2/canvas/page-1.json"}]}]}]}