Date of Award
Doctor of Philosophy
Richard C. Larock
A novel synthetic methodology for 9-alkylidene-9H-fluorenes by the palladium-catalyzed 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-3,4--diphenylnaphthalene 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-(E)-1-propenyl-4-propylnaphthalene has been obtained as the sole product in the reaction of 4-octyne. 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 Z,Z-ethylene glycol dioleate afforded the isomerized E,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 rubbers, have been prepared from the ADMET polymerization of soybean oil under different conditions. These materials are very likely to be biodegradable and have potential applications in paints, lubricants, coatings and adhesives.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Tian, Qingping, "Palladium-catalyzed annulation of alkynes and ADMET polymerization of soybean oil " (1998). Retrospective Theses and Dissertations. 12545.