Iron-Catalyzed Arylsulfonylation of Activated Alkenes

Abstract

An efficient iron-catalyzed arylsulfonylation of activated alkenes has been developed. The protocol uses readily available N-acryl-N-substituted benzenesulfonamides and arylsulfinic acids as the starting materials, inexpensive iron salt as the catalyst, and environmentally friendly oxygen in air as the oxidant. α-Aryl-β-sulfonyl amides containing a quarternary stereocenter were obtained using N-acryl-N-alkyl benzenesulfonamides as the substrates.

Key words

iron - catalysis - arylsulfonylation - alkenes - domino reaction

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• 20 General Procedure for the Synthesis of α-aryl-β-Sulfonyl Amides 3a–q or Sulfonylated Oxindoles 4a–l A 25 mL Schlenk tube was charged with a magnetic stirrer and THF (2.5 mL). N-Acryl-N-aryl benzenesulfonamide (1, 0.25 mmol), arylsulfinic acid (2, 0.75 mmol; 0.4 mmol of 2 were added for the first time; after 12 h, 0.35 mmol of 2 were added for the second time), and FeSO₄·7H₂O (0.025 mmol, 7 mg) were added to the tube. The tube was sealed, and the mixture was stirred at 100 °C for 24 or 36 h in the presence of air. The resulting mixture was cooled to r.t., the solvent was removed by a rotary evaporator, and the residue was purified by column chromatography on silica gel using PE–EtOAc as the eluent to give the desired target product 3 or 4. Four representative examples are shown as follows: 2-Methyl-N,2-diphenyl-3-(phenylsulfonyl)propanamide (3a) Eluent: PE–EtOAc (3:1); yield 67 mg (71%); white solid; mp 134–137 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.67 (d, 2 H, J = 7.3 Hz), 7.52 (t, 1 H, J = 7.8 Hz), 7.41–7.25 (m, 11 H), 7.09 (t, 1 H, J = 7.3 Hz), 6.91 (s, 1 H), 4.02 (q, 2 H), 2.15 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 172.8, 141.4, 139.6, 137.6, 133.4, 129.3, 129.2, 128.5, 127.8, 127.3, 124.9, 120.4, 64.3, 50.6, 22.9. ESI-MS: m/z = 380.2 [M + H]⁺, 402.2 [M + Na]⁺. 2-Methyl-3-(phenylsulfonyl)-2-(p-tolyl)-N-[4-(trifluoromethyl)phenyl]propanamide (3n) Eluent: PE–EtOAc (5:1); yield 83 mg (72%); white solid; mp 145–147 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.64 (d, 2 H, J = 8.2 Hz), 7.53–7.46 (m, 5 H), 7.37 (t, 2 H, J = 7.3 Hz), 7.21 (s, 1 H), 7.04 (d, 2 H, J = 8.2 Hz), 3.97 (q, 2 H), 2.29 (s, 3 H), 2.11 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 173.3, 141.1, 140.7 138.4, 136.1, 133.3, 130.0, 129.9, 127.7, 126.9, 126.3 (q, J = 23.8 Hz), 124.1 (q, J = 273.2 Hz), 119.9, 64.3, 50.3, 22.7, 21.2. ¹⁹F NMR (376 MHz, CDCl₃): δ = –63.0. ESI-MS: m/z = 462.2 [M + H]⁺. 1-Isopropyl-3-methyl-3-[(phenylsulfonyl)methyl]indolin-2-one (4c) Eluent: PE–EtOAc (3:1); yield 43 mg (50%); light yellow solid; mp 181–184 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.52–7.49 (m, 3 H), 7.36 (t, 2 H, J = 6.9 Hz), 7.21 (t, 1 H, J = 7.8 Hz), 7.04 (d, 1 H, J = 8.2 Hz), 6.91 (d, 1 H, J = 7.3 Hz), 6.77 (t, 1 H, J = 7.8 Hz), 4.73–4.63 (m, 1 H), 3.76 (q, 2 H), 1.55 (d, 3 H, J = 6.4 Hz), 1.51 (d, 3 H, J = 6.4 Hz), 1.36 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 177.6, 142.3, 140.7, 133.4, 130.2, 129.2, 128.5, 127.8, 124.2, 122.1, 110.4, 62.2, 45.6, 44.3, 25.8, 19.6, 19.1. ESI-MS: m/z = 344.1 [M + H]⁺. 1,3,5-Trimethyl-3-({[4-(trifluoromethyl)phenyl]sulfonyl}methyl)indolin-2-one (4i) Eluent: PE–EtOAc (3:1); yield 66 mg (66%); light yellow solid; mp 137–139 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.58 (d, 2 H, J = 8.6 Hz), 7.49 (d, 2 H, J = 8.3 Hz), 7.05 (d, 1 H, J = 7.9 Hz), 6.75 (d, 1 H, J = 7.9 Hz), 6.53 (s, 1 H), 3.84 (q, 2 H), 3.19 (s, 3 H), 2.06 (s, 3 H), 1.35 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 177.5, 143.5, 141.4, 132.2, 129.4, 129.1, 128.6, 125.9 (q, J = 3.6 Hz), 124.7, 123.3 (q, J = 273.1 Hz), 108.5, 62.2, 45.7, 26.8, 25.6, 20.8. ¹⁹F NMR (376 MHz, CDCl₃): δ = –63.9. ESI-MS: m/z = 398.2 [M + H]⁺.
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