Di-tert-butyliminoxy, a free radical of moderate stability

Oxime Radical Promoted Dioxygenation, Oxyamination, and Diamination of Alkenes: Synthesis of Isoxazolines and Cyclic Nitrones

“…The free radical cyclization reactions have found wide applications in the synthesis of carbo-and heterocyclic compounds. [7] The physical properties such as structure, stability, and spectroscopy of oxime radicals have been extensively studied since then. However, to the best of our knowledge the participation of an oxime radical in reactions has not been reported so far.…”

“…[5] Oxime radicals were first identified by Thomas using EPR spectroscopy as early as 1964, [6] and Ingold et al isolated and studied the di-tert-butyliminoxyl radical in 1971. [7] The physical properties such as structure, stability, and spectroscopy of oxime radicals have been extensively studied since then. [8] Given our continued interest in the aminoxyl radical mediated reactions, [9] we report herein the first 5-exo-trig cyclization of b,g-unsaturated oximes involving an oxime radical, a reaction which was initiated by commercially available TEMPO or DEAD (diethyl azodicarboxylate).…”

Iminoxyl Radical‐Based Strategy for Intermolecular CO Bond Formation: Cross‐Dehydrogenative Coupling of 1,3‐Dicarbonyl Compounds with Oximes

“…[98][99][100][101][102][103] However, only a few reactions with oxime (iminoxyl) radicals were described in the literature. The synthetic application of these radicals has long been limited to reactions of the stable di-tert-butyliminoxyl radical: [99,100] the oxidation of amines to imines, [104] the oxidative addition to phenols, [105] and the replacement of allylic hydrogen in cyclohexene. [106] First selective reactions involving unstable iminoxyl radicals generated in situ were realized only recently: the intramolecular hydrogen atom abstraction by oxime radical followed by cyclization [107] and the intramolecular addition to the C=C double bond [108] were performed.…”

Di-(1-adamantyl)iminoxy. Preparation and Dipole Moment

“…Di-t-butyliminoxy, (t-Bu),C=NO., was pre-oxy, (I-Ad),C=NO., from the parent imine3 (3) pared in these laboratories a few years ago (1). by the procedure used for (t-Bu),C=NO.…”

“…117-1 18"; n.m.r. 1.67 (12 H), 1 While various assunlptions could be made about the detailed structures of these compounds and the individual bond moments, we feel that, so far as the question of electron delocalization goes, the following approach is justified by its simplicity. For (1-Ad),C=NOMe, we take the C=N-0 angle to be ca.…”