While organocuprate reagents have been a staple in synthetic organic chemistry in the formation of carbon-carbon bonds, there has been a dearth of investigations into its use in forming carbon-heteroatom bonds. In previous cases of complexes between organocuprates and carbon-heteroatom π-bonds, the reaction generally proceeds in a carbophilic manner. In particular, there is a great desire for the utilization of organocuprates in the electrophilic amination of carbanions, adding another tool for carbon-nitrogen bond formation for the synthetic chemist. To provide an understanding of the inherent directional preference seen in these cuprate reactions, a series of experiments investigating the reaction between dimethyl cuprates and a variety of substrates containing nitrogen-nitrogen π-bonds were performed. Using an experimental technique called Rapid Injection NMR, the intermediates and pathways of these reactions will be characterized and evaluated.
In a second part, investigations will be carried out into the β-silylation of β-aryl-α,β-unsaturated carbonyls with organocuprates in the presence of silyl chlorides and silyl cyanides. While this β-silylation has been noted in the literature to only occur with copper (I) cyanide as the starting copper salt, and with an aryl substituent in the β-position, little work has been done into probing the mechanism of this reaction. Utilizing Rapid Injection NMR, a cyanocuprate (III) intermediate was observed, which reacted with a second equivalent of silane in solution form the β-silyl product and an equivalent of ethane, from the reductive elimination of the methyl groups.
|Commitee:||Etzkorn, Markus, Murphy, Michael, Nesmelova, Irina|
|School:||The University of North Carolina at Charlotte|
|School Location:||United States -- North Carolina|
|Source:||MAI 55/05M(E), Masters Abstracts International|
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