486999-99-9Relevant academic research and scientific papers
Intra- and intermolecular trapping of cyclopentapyrazine carbenes derived from 1,2-dialkynylimidazoles
Nadipuram, Asha K.,Kerwin, Sean M.
, p. 353 - 356 (2006)
The thermolysis of 1,2-dialkynylimidazoles in benzene solution affords high yields of 7-phenyl-5H-cyclopentapyrazines, which presumably form by solvent trapping of cyclopentapyrazine carbene intermediates. In cases where dialkynylimidazole contains side chains that can participate in intramolecular carbene C-H insertion or olefin addition, these processes compete with solvent addition to afford novel tri- and tetracyclic pyrazines, which can be obtained in good yield when the thermolysis is carried out in hexafluorobenzene.
Cytotoxic 1,2-dialkynylimidazole-based aza-enediynes: Aza-Bergman rearrangement rates do not predict cytotoxicity
Laroche, Christophe,Li, Jing,Kerwin, Sean M.
scheme or table, p. 5059 - 5069 (2011/10/02)
A new class of potential antitumor agents inspired by the enediyne antitumor antibiotics has been synthesized: the 1,2-dialkynylimidazoles. The aza-Bergman rearrangement of these 1,2-dialkynylimidazoles has been investigated theoretically at the B3LYP/6-3
Thermal cyclization of 1,2-dialkynylimidazoles to imidazo[1,2-a]pyridines
Nadipuram, Asha K.,Kerwin, Sean M.
, p. 3798 - 3808 (2007/10/03)
Thermolysis of 1,2-dialkynylimidazoles in chlorinated solvents leads to 5-chloroimidazo[1,2-a]-pyridine products, which are also formed in DMF containing 1 equiv of HCl. Deuterium labeling of the starting dialkynylimidazoles indicates that reaction may proceed by multiple pathways, depending upon conditions and substituents. Dialkynylimidazoles can also give rise to 5-diethylamino-substituted imidazopyridines when the thermolysis is carried out in the presence of diethylamine.
Synthesis and thermolysis of heterocyclic 3-aza-3-ene-1,5-diynes(1).
Nadipuram, Asha K,David, Wendi M,Kumar, Dalip,Kerwin, Sean M
, p. 4543 - 4546 (2007/10/03)
[reaction: see text] Simple, acyclic 3-aza-3-ene-1,5-diynes undergo an aza-Bergman rearrangement to a fleeting 2,5-didehydropyridine (2,5-ddp) intermediate that rapidly ring-opens to beta-alkynylacrylonitrile products. In an effort to access longer-lived 2,5-ddp intermediates, we have prepared heterocyclic 3-aza-3-ene-1,5-diynes. The thermolysis of one such heterocyclic aza-enediyne does not afford products derived from trapping a 2,5-ddp intermediate but rather cyclopropanes that appear to arise from a carbene intermediate and a product that appears to be a trapping product from a 2,3-ddp intermediate.
