|Thesis Title||Synthesis of α,β-Unsaturated Carbonyl Compounds Using Organoselenium Reagents.|
Jim's first project involved a test for cyclic conjugation of carbonium ions in spiro-fused cyclopropane rings. He compared the rates of formation of the cation 1 with 2 and 3. A small rate acceleration of 70 for 2 was found attributable to cyclic delocalization, after correction for the inductive effect of the double bond..
Jim then began a very productive investigation of a number of facets of the use of the selenoxide elimination for the synthesis of enones (first discovered by Ieva Reich). He greatly extended the generality of the synthetic method by establishing the principal side reactions that occurred, and developing experimental protocols that avoided these side reactions.
During these studies he first prepared N,N-dialkylselenenamides, and examined their chemistry.
Jim also investigated the use of bromomethyl selenides as alkylating agents for carbonyl enolates, a reaction later used effectively by Craig Jasperse in his work on selenocysteine analogs.
Senior Research Scientist, Discovery Process Research|
DowElanco Discovery Process