Visible-Light-Mediated Direct Amidation of Arenes and Hetero­arenes with N-Aminopyridinium Salts

Abstract

A novel photoinduced strategy has been developed for the C–H amidation of aromatics and heteroaromatics by using benzamide radicals with free NH groups generated from N-amidopyridinium salts under visible-light irradiation. The new mode of activation of N-amidopyridinium salts proceeds efficiently under mild conditions to give various benzamide derivatives with free NH groups. In addition, oxazoline analogues, synthesized by the reaction with styrene, demonstrate a substantial range of prospective applications for this versatile protocol.

Key words

photocatalysis - amidopyridinium salts - amidation - [3+2]-annulation - radical reactions

• References and Notes

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• 14 Amidation Reaction: General Procedure A vacuum-dried photoreaction tube was charged with N-(benzoylamino)-2,4,6-triphenylpyridinium tetrafluoroborate (1; 0.3 mmol, 1.0 equiv), coupling agent 2 (3 mmol, 10.0 equiv), Ru(bpy)₃Cl₂ (5 mol%), and anhyd MeCN (3 mL). The tube was then purged with Ar for 10–15 min, then sealed. The mixture was then stirred and uniformly irradiated by a 30 W blue-light lamp 24 h until the starting material was completely consumed. All volatiles were removed from the resulting mixture in a rotary evaporator under reduced pressure and the crude product was purified by column chromatography. 1-Benzoyl-2-methyl-4-phenyl-4,5-dihydro-1H-imidazole (3n); Typical Procedure for a [3+2]-Annulation Reaction A vacuum-dried photoreaction tube was charged with N-(benzoylamino)-2,4,6-triphenylpyridinium tetrafluoroborate (1; 0.3 mmol, 1.0 equiv), styrene (2n; 0.3 mmol, 1.0 equiv), Ru(bpy)₃(PF₆)₂ (5 mol%), and anhyd MeCN (3 mL, 10 equiv). The tube was then purged with Ar for 10–15 min, then sealed. The mixture was then stirred and uniformly irradiated by a 30 W blue-light lamp for 24 h. Soon afterward, the resulting mixture was concentrated by vacuum distillation in a rotary evaporator. Column chromatography [silica gel, PE–EtOAc (2:1)] gave a pale yellow oily liquid; yield: 70.7%; R_f = 0.3 (PE–EtOAc). ¹H NMR (600 MHz, CDCl₃): δ = 7.48 (d, J = 7.2 Hz, 2 H), 7.43 (t, J = 7.4 Hz, 1 H), 7.36 (t, J = 7.5 Hz, 2 H), 7.28 (t, J = 7.5 Hz, 2 H), 7.22 (d, J = 7.3 Hz, 1 H), 7.20 (s, 2 H), 5.04 (t, J = 8.8 Hz, 1 H), 4.20 (t, J = 10.3 Hz, 1 H), 3.70 (dd, J = 10.6, 8.2 Hz, 1 H), 2.28 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 168.66, 159.34, 141.69, 135.96, 131.31, 128.81, 128.60, 127.69, 127.39, 126.49, 67.20, 56.75, 18.67. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₇H₁₇N₂O: 265.1336; found: 265.1340.