Carbene and diradical-generating cyclizations of dialkynyl azoles
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Study of the aza-Bergman rearrangement was expanded to include thermolysis of the 1,2-dialkynylpyrrole (1,2-DAP) and a 1,5-dialkynylpyrazole (1,5-DAPz). The product obtained from thermolysis of 1,2-DAP was a six-membered pyridine-containing species, resulting from the rearrangement of the starting 1,2-DAP to a cumulene intermediate and then finally to a carbene-containing species. After performing kinetics experiments of the thermolysis with the 1,2-DAP, the resulting experimental calculations were found to be within good agreement of theoretical calculations for the aza-Bergman rearrangement. Thermolysis of a 1,5-DAPz, however, resulted in a variety of different products. The mechanism of formation behind these products have not been confirmed, but several possibilities are put forth.