N-(ortho-Aryloxyphenyl)arylimidoyl radicals: Novel 1,5-aryl radical translocation from oxygen to carbon

Synthesis using aromatic homolytic substitution—recent advances

“…99 Di(isopropyl) dicarboxylate (DPDC) has been used for the abstraction of hydrogen from imines to generate imidoyl radicals. 133 Cobalt(II) complexes have been used for generating radicals for aromatic homolytic substitution. The synthesis of toddaquinoline shown in Scheme 22 has been carried out with cobalt reagents.…”

Late-Stage Two-Step C11–H Arylation of Dibenzooxa/thiazepines

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.64 (d, J = 7.6 Hz, 2 H), 7.38 (t, J = 7.6 Hz, 1 H), 7.34 (dd, J = 7.2, 2.4 Hz, 1 H), 7.20-7.16 (m, 3 H), 7.12-7.02 (m, 5 H), 2.37 (s, 3 H). 13 28 Prepared according to the two-step procedure; white solid; yield: 256 mg (85%); mp 94-96 °C; R f = 0.40 (PE/EtOAc 10:1 v/v).…”

“…1 H NMR (400 MHz, CDCl3, δ): 7.76 (d, J = 8.8 Hz, 2H), 7.47 (td, J = 7.2, 1.6 Hz, 1H), 7.42 -7.38 (m, 1H), 7.30 (dd, J = 7.6, 1.6 Hz, 1 H), 7.27 (dd, J = 8, 1.6 Hz, 1 H), 7.19 -7.10 (m, 4H), 6.73 (d, J = 8.8 Hz, 2H), 3.05 (s, 6H).13 C{ 1 H} NMR (101 MHz, CDCl3, δ): 166.7, 162.1, 152.7, 152.1, 141.5, 132.6, 131.7, 131.3, 127.9, 127.61, 127.57, 126.5, 125.5, 124.4, 120.9, 120.6, 111.3, 40.3. HRMS (ESI) m/z: [M + H] + calcd for C21H19N2O + , 315.1492; found, 315.1485.11-(4-Fluorophenyl)dibenzo[b,f][1,4]oxazepine (4e)Prepared according to the two-step procedure.HRMS (ESI) m/z: [M + H]+ calcd for C19H13FNO + , 290.0976; found, 290.0968.11-(4-Chlorophenyl)dibenzo[b,f][1,4]oxazepine (4f)28 [124293-60-3] Prepared according to the two-step procedure. Light yellow solid, 220 mg, yield 72%, mp 137-138 °C, Rf = 0.30 (PE/EA = 20:1, v/v).111-(o-Ttolyl)dibenzo[b,f][1,4]oxazepine (4h)Prepared according to the two-step procedure.Light yellow solid, 223 mg, yield 78%, mp 85-86 °C, Rf = 0.40 (PE/EA = 20:1, v/v).1 H NMR (400 MHz, CDCl3, δ): 7.56 (dd, J = 7.6, 1.6 Hz, 1H), 7.50 -7.46 (m, 2H), 7.39 (qd, J = 7.6, 1.6 Hz, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.30 -7.20 (m, 5H), 7.10 (td, J = 7.6, 1.2 Hz, 1H), 6.97 (dd, J = 8.0, 2.0 Hz, 1H), 2.29 (s, 3H).…”

Photocatalytical and Photochemical Generation of Imidoyl Radicals: Synthetic Applications

“…Amongst them, their generation from isocyanides remains a primary mode of their occurrence, despite that fact that the first report of their formation entailed homolytic fission. [5] Once formed, an imidoyl radical may proceed in one of the following ways-(i) add to the unsaturated systems to access N-heterocycles or acyclic imine precursors, [6] (ii) undergoes β-scission to nitriles, [7] or (iii) undergoes SET oxidation/reduction to give nitrilium cation [8] /imidoyl anion [9] which finally can get trapped by a nucleophile/electrophile respectively. It's interesting to observe that an imidoyl radical generated from an isocyanide can revert back to the parent compound via an α-scission and this reversibility is something to watch for during chemistry involving imidoyl radicals, as shown in Figure 1.…”