Palladium-catalyzed annulation of alkynes and ADMET polymerization of soybean oil

Abstract

A novel synthetic methodology for 9-alkylidene-9H-fluorenes by the palladiumcatalyzed cascade reaction of aryl iodides and internal alkynes has been developed. This methodology has been extended to a number of aryl iodides and internal alkynes. The synthesis of a 9-alkylidene-9H-fluorene has also been achieved from a vinylic iodide. It has been demonstrated that this unusual cascade migration/coupling process also provides an efficient synthetic route to polycyclic aromatic hydrocarbons. We have also investigated the palladium-catalyzed reaction of internal alkynes and (2-iodophenyl)acetonitrile or 2-iodobenzonitrile. (2-Iodophenyl)acetonitrile reacts with diphenylacetylene in the presence of a palladium catalyst to afford 2-amino-3.4diphenylnaphthalene in 83% yield. This is the first example of a cyano group actually participating in an organopalladium addition reaction. An unusual product 2-amino-3-{(£')l-propenyl }-4-propylnaphthalene has been obtained as the sole product in the reaction of 4octyne. The formation of this unusual product has been rationalized by a mechanism similar to the palladium-catalyzed cyclization of enynes. The reaction of 2-iodobenzonitrile and diphenylacetylene affords 2.3-diphenylindenone in 30% yield. The acyclic diene metathesis (ADMET) polymerization of soybean oil has been studied in this thesis. The polymerization of ethylene glycol dioleate afforded the isomerized E,£-dioleate (27%), dimer (18%), trimer (13%), tetramer (7%), pentamer (5%), hexamer (4%), heptamer (4%) and 9-octadecene (21%). Only a trace amount of the intramolecular cyclized compound (0.1 %) was formed in the reaction. Under the same conditions, glyceryl trioleate undergoes ADMET polymerization to produce dimer, trimer. tetramer, pentamer and monocyclic oligomers, with monocyclic oligomers predominating. A variety of materials, from sticky oils to mbbers, have been prepared from the ADMET