Synthesis and thermolysis of heterocyclic 3-aza-3-ene-1,5-diynes(1).
[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.
Nadipuram
Asha K
AK
Division of Medicinal Chemistry, College of Pharmacy, The University of Texas at Austin, 78712, USA.
David
Wendi M
WM
Kumar
Dalip
D
Kerwin
Sean M
SM
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
D000480:Alkynes; D000970:Antineoplastic Agents; D001562:Benzimidazoles; D003521:Cyclopropanes; C030797:cyclopropane; C031000:benzimidazole