Remote Oxidative C–H Amidation of Anilides with Dibenzenesulfonimides under Metal-Free Conditions

Abstract

General Information1 H NMR, 13 C NMR spectra were recorded on a Bruker DPX-400 spectrometer with CDCl 3 as the solvent and TMS as an internal standard, operating at 400 MHz for 1 H NMR and 100 MHz for 13 C NMR. Melting points were measured by SGW X-4A microscopic apparatus. HRMS-ESI were measured by Q Exactive LC/HRMS spectrometer. Ethyl acetate and hexane were obtained from commercial sources and used for column chromatography without further purification. Other solvents were purified according to the standard methods. Other chemicals were obtained from commercial sources and used as received unless otherwise noted. All the anilides were synthesized through the coupling between corresponding aryl or alkyl acids and anilines according to previous procedures. 1 White solid, 64.0 mg, 72% yield, °C; 1 H NMR (400 MHz, CDCl 3 ): δ 2.14 (s, 3H), 2.18 (s, 3H), 6.79-6.84 (m, 2H), 7.21 (s, 1H), 7.54 (t, J = 7.54 Hz, 4H), 7.67 (t, J = 7.36 Hz, 2H), 7.92 (d, J = 7.92 Hz, 4H), 7.98 (d, J = 8.48 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 17. 63, 24.57, 122.40, 128.52, 129.06, 129.81, 130.09, 133.23, 133.53, 134.03, 137.86, 139.30, 168.52. HRMS-ESI(m/z): calcd for C 21 H 21 N 2 O 5 S 2 (M+H + ): 445.0886, found 445.0884. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)propionamide (3b)White solid, 65.0 mg, 71% yield, mp 185-186 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 1.22 (t, J = 7.44 Hz, 3H), 2.14 (s, 3H), 2.41 (q, J = 7.39 Hz, 2H), 6.80 (d, J = 8.64 Hz, 1H), 6.84 (s, 1H), 7.22 (s, 1H), 7.54 (t, J = 7.58 Hz, 4H), 7.67 (t, J = 7.28 Hz, 2H), 7.91 (d, J = 8.. HRMS-ESI(m/z): calcd for C 22 H 23 N 2 O 5 S 2 (M+H + ): 459.1043, found 459.1045. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)isobutyramide (3c) White solid, 69.9 mg, 74% yield, mp 166-167 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 1.25 (s, 3H), 1.27 (s, 3H), 2.18 (s, 3H), 2.53-2.61 (m, 1H), 6.81 (d, J = 8.72 Hz, 1H), 6.86 (s, 1H), 7.14 (s, 1H), 7.55 (t, J = 7.56 Hz, 4H), 7.65-7.70 (m, 2H), 7.93 (d, J = 7.96 Hz, 4H), 8.06 (d, J = 8.. HRMS-ESI(m/z): calcd for C 23 H 25 N 2 O 5 S 2 (M+H + ): 473.1199, found, 473.1195. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)cyclopropanecarboxamide(3d)White solid, 59.2 mg, 63% yield, mp 185-187 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 0.86 (d, J = 4.92 Hz, 2H), 1.08 (s, 2H), 1.55-1.59 (m, 1H), 2.19 (s, 3H), 6.78 (d, J = 8.56 Hz, 1H), 6.85 (s, 1H), 7.35 (s, 1H), 7.54 (t, J = 7.54 Hz, 4H), 7.67 (t, J = 7.36 Hz, 2H), 7.97 (d, J = 7.88 Hz, 4H), 8.03 (s, 1H); 13 Light yellow solid, 68.4 mg, 64% yield, mp108-110 °C; 1 H NMR (500 MHz, CDCl 3 ): δ 1.97 (s, 3H), 2.68-2.75 (m, 2H), 3.07 (t, J = 7.35 Hz, 2H), 6.78-6.84 (m, 2H), 7.20-7.34 (m, 6H), 7.50-7.61 (m, 5H), 7.65-7.69 (m, 2H), 7.91-7.94 (m, 3H), 8.00 (d, J = 7.35 Hz, 1H); 13 (m/z): calcd for C 28 H 27 N 2 O 5 S 2 (M+H + ): 535.1356, found 535.1353. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)benzamide (3f) White solid, 67.8 mg, 67% yield, mp 167-169 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 2.28 (s, 3H), 6.87 (d, J = 8.64 Hz, 1H), 6.91-6.96 (m, 1H), 7.48-7.51 (m, 2H), 7.5...

(Diacetoxy)iodobenzene-Mediated Regioselective Imidation of Imidazoheterocycles with N-Fluorobenzenesulfonimide

“…On the basis of the control experiments (Scheme 5) as well as previous reports, 4c,18,20 a plausible mechanism of PIDA-mediated C–H imidation of imidazopyridines with NFSI is presented in Scheme 6. Probably, the first step is the PIDA-mediated oxidation of imidazopyridine ( 1a ) to imidazopyridine radical cation ( A ) along with the formation of radical ( B ) through a single electron-transfer process.…”

One-pot access to 11-methyl-6H-indolo[2,3-b]quinolines via iodine-mediated annulation of indoles with 2-vinylanilines and evaluation of their biological activities

“…14 Meanwhile, various reagents based on iodine are constantly being developed and applied. 15 As continuation of our ongoing research on organoiodine 16 and N-heterocycles, 17 herein, we now present our discoveries in iodine-mediated efficient synthesis of diverse 11-methyl-6 H -indolo[2,3- b ]quinolines via annulation of indoles with 2-vinylanilines. Besides, our newly synthesized 11-methyl-6 H -indolo[2,3- b ]quinoline derivatives showed promising cytotoxic and antiviral activities in biological evaluations.…”