title: Synthesis and thermolysis of heterocyclic 3-aza-3-ene-1,5-diynes(1).
abstract: [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.
authors.affiliation: Division of Medicinal Chemistry, College of Pharmacy, The University of Texas at Austin, 78712, USA.
authors.forename: Asha K
authors.initials: AK
authors.lastname: Nadipuram
authors.forename: Wendi M
authors.initials: WM
authors.lastname: David
authors.forename: Dalip
authors.initials: D
authors.lastname: Kumar
authors.forename: Sean M
authors.initials: SM
authors.lastname: Kerwin
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry*; D000970:Antineoplastic Agents / Q000138:chemical synthesis* / Q000737:chemistry*; D001562:Benzimidazoles / Q000138:chemical synthesis / Q000737:chemistry; D003500:Cyclization; D003521:Cyclopropanes / Q000737:chemistry; D015195:Drug Design; D015394:Molecular Structure
chemical_list: D000480:Alkynes; D000970:Antineoplastic Agents; D001562:Benzimidazoles; D003521:Cyclopropanes; C030797:cyclopropane; C031000:benzimidazole