Thermal decomposition of tert-butyl ortho-(phenylsulfanyl)- and ortho-(phenylsulfonyl)phenyliminoxyperacetates: The reactivity of thio-substituted iminyl radicals

Abstract

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Gas-phase cyclisation reactions of 1-(2-arylthiophenyl)alkaniminyl and 2-(aryliminomethyl)thiophenoxyl radicals

“…This product was also a major component from the solution-phase study. 4 In addition, a small amount of the nitrile 30 (8%) was isolated; the presence of the nitrile function was confirmed by IR spectroscopy (ν max 2219 cm Ϫ1 ) and by comparison with literature data. 16 Pyrolysis of the anil 19 gave the same set of radical coupling products as its analogue 18 (viz.…”

“…The following component was also impure (≈10%), but again showed a molecular ion at m/z 211, though in this case a singlet at δ H 8.91 (corresponding to the CH of an imine function) was present. This compound may be the dibenzo[b,f] [1,4]thiazepine 31 [δ H (lit., 13 ) 8.7] but the literature data for this compound are insufficiently precise to make an unambiguous identification. Nevertheless, this result defines the maximum limit of seven-membered ring formation in this study (cf.…”

“…The corresponding solution-phase behaviour of the iminyls was reported in the preceding paper in this issue. 4…”

Copper-catalyzed oxidative benzylic C-H cyclization via iminyl radical from intermolecular anion-radical redox relay

“…Herein, we report our recent results in the probe of the copper-catalyzed anion-radical redox relay, we initialize the reaction by a base-promoted benzylic C-H cleavage to generate the benzyl anion A , which passes through a Cu(II)-mediated oxidation to radical B 5 . The intermolecular radical addition of B to PhCN generates iminyl radial C , which is trapped by aryl ring to form D 65–67 . D is reduced by Cu(I) to indoles with the regeneration of Cu(II) (Fig.…”

Light-Induced Iminyl Radicals: Generation and Synthetic Applications

“…In this case, the formation of the iminyl radical takes place after a double decarboxylation (Boivin et al, 1994). An analogous thermal decomposition procedure involving decarboxylation and loss of formaldehyde to obtain an iminyl radical has been also described from peresters (Leardini et al, 2001). Although not used from a synthetic point of view, ketoxime diurethanes also lead to the formation of radicals (Hwang et al, 1999).…”