Radical and Nitrenoid Reactivity of 3-Halo-3-phenyldiazirines

• DOI: 10.1021/acs.orglett.6b01753
• Publication Date: 2016-07-20T20:40:32Z
• Authors: Rafael Navrátil; Ján Tarábek; Igor Linhart; Tomáš Martinů
• Keywords: Reactivity

3-Halo-3-phenyl-3H-diazirines (halogen = Br or Cl) undergo a dissociative single-electron transfer from alkyllithiums (RLi) in THF-based solvent mixtures. The resulting 3-phenyldiazirinyl radical, observed by EPR spectroscopy, is eventually transformed to benzonitrile. In Et2O, 2 equiv of RLi add both nitrogens halodiazirine N═N bond, affording N,N'-dialkylbenzamidines. nitrenoid reactivity some N-alkyl-1H-diazirine intermediates manifested their insertion into the α-C-H bond THF Et2O.