Copper-Catalyzed Asymmetric Intermolecular N-Monoarylation of Unprotected Sulfonamides via Desymmetrization of Diaryliodonium Salts at Room Temperature

Abstract

A copper-catalyzed asymmetric intermolecular N-monoarylation of weakly nucleophilic sulfonamide by desymmetrization of cyclic diaryliodonium salts has been developed. Chiral copper(II)–diamine ligand complexes catalyzed this intermolecular asymmetric aryl C–N cross-coupling reaction effectively at room temperature to afford a series of N-monoarylsulfonamides in good to excellent yields and enantioselectivities.

Key words

asymmetric synthesis - copper-catalyzed - N-monoarylation - sulfonamide - diaryliodonium salt - desymmetrization

• References and Notes


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• 16 General Procedure for the Asymmetric Intermolecular N-Arylation of Sulfonamide The diaryliodonium salt 1 (0.25 mmol, 1.0 equiv), sulfonamide 2 (0.30 mmol, 1.2 equiv), catalyst (0.025 mmol, 10 mol%), ligand L1 (0.0375 mmol, 15 mol%), and base (0.5 mmol, 2.0 equiv) were added to a 10 mL oven-dried Schlenk tube, followed by addition of anhydrous 1,2-dichloroethane (1.5 mL) under argon atmosphere. The mixture was stirred at room temperature for 15 h. Then the reaction mixture was poured into water (1.5mL) and extracted with dichloromethane (3 × 5 mL). The combined organic phase dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by flash chromatography (silica gel, petroleum ether/ethyl acetate = 5:1) to give the desired product 3. (S)-Ethyl 3-(2-Iodophenyl)-3-[2-(phenylsulfonamido)phenyl]propanoate (3a) Yield 128.3 mg (96%); white solid, mp 83.4–84.2 °C; [α]_D ²⁵ –13.4 (c 0.35, CHCl₃, 88% ee). HPLC Chiralpak AD-H (hexane/i-PrOH = 6:4, 1.0 mL/min): τ_major = 14.7 min, τ_minor = 10.0 min. ¹H NMR (400 MHz, CDCl₃): δ = 7.84 (d, J = 7.6 Hz, 1 H), 7.75 (d, J = 7.2 Hz, 2 H), 7.54 (d, J = 7.6 Hz, 1 H), 7.46 (t, J = 7.6 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 2 H), 7.23–7.18 (m, 2 H), 7.17–7.10 (m, 2 H), 7.01 (br s, 1 H), 6.96–6.90 (m, 2 H), 4.67 (dd, J = 9.2, 6.0 Hz, 1 H), 4.08–3.99 (m, 2 H), 2.87 (dd, J = 16.0, 6.0 Hz, 1 H), 2.62 (dd, J = 16.4, 9.2 Hz, 1 H), 1.10 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.0, 143.9, 140.3, 140.0, 134.8, 133.4, 132.8, 129.0, 129.0, 128.8, 128.5, 127.9, 127.8, 127.2, 125.6, 123.2, 101.1, 60.9, 45.3, 40.1, 14.1. ESI-MS: m/z = 558.0 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₃H₂₂INNaO₄S: 558.0206; found: 558.0207. (S)-Ethyl 3-(2-Iodophenyl)-3-[2-(2-methylphenylsulfonamido)phenyl]propanoate (3b) Yield 129.0 mg (94%); white solid, mp 82.3–83.2 °C; [α]_D ²⁵ –6.5 (c 0.95, CHCl₃, 87% ee). HPLC Chiralpak AD-H (hexane/i-PrOH = 7:3, 1.0 mL/min): τ_major = 11.1 min, τ_minor = 10.3 min. ¹H NMR (400 MHz, CDCl₃): δ = 7.98 (dd, J = 8.0, 1.2 Hz, 1 H), 7.85 (dd, J = 8.0, 1.2 Hz, 1 H), 7.41 (t, J = 7.6 Hz, 1 H), 7.30–7.25 (m, 3 H), 7.22 (br s, 1 H), 7.20 (dd, J = 8.0, 1.6 Hz, 1 H), 7.15–7.04 (m, 4 H), 6.94 (td, J = 8.0, 1.6 Hz, 1 H), 4.87 (dd, J = 9.6, 6.4 Hz, 1 H), 4.10–4.04 (m, 2 H), 2.95 (dd, J = 16.4, 6.0 Hz, 1 H), 2.75 (dd, J = 16.4, 9.2 Hz, 1 H), 2.58 (s, 3 H), 1.13 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.3, 144.1, 140.3, 139.0, 137.5, 135.1, 132.9, 132.8, 132.7, 129.4, 129.0, 128.7, 128.3, 127.9, 127.7, 126.3, 125.1, 122.1, 101.3, 60.9, 45.2, 40.2, 20.4, 14.0. ESI-MS: m/z 572.0 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₄H₂₄INNaO₄S: 572.0363; found: 572.0363. (S)-Ethyl 3-[2-(3-Bromophenylsulfonamido)phenyl]-3-(2-iodophenyl)propanoate (3c) Yield 118.2 mg (77%); white solid, mp 154.2–154.7 °C; [α]_D ²⁵ –6.8 (c 0.31, CHCl₃, 86% ee). HPLC Chiralpak AD-H (hexane/i-PrOH = 7:3, 1.0 mL/min): τ_major = 15.8 min, τ_minor = 10.3 min. ¹H NMR (400 MHz, CDCl₃): δ = 7.93 (t, J = 1.6 Hz, 1 H),7.85 (d, J = 8.0 Hz, 1 H), 7.63 (d, J = 7.6 Hz, 1 H), 7.55 (t, J = 8.0 Hz, 2 H), 7.25–7.15 (m, 5 H), 7.09 (br s, 1 H), 6.94–6.90 (m, 2 H), 4.63 (dd, J = 10.0, 5.2 Hz, 1 H), 4.10–4.01 (m, 2 H), 2.90 (dd, J = 16.8, 5.6 Hz, 1 H), 2.72 (dd, J = 16.4, 10.0 Hz, 1 H), 1.11 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.1, 143.8, 141.7, 140.4, 135.9, 134.5, 133.6, 130.5, 130.0, 129.1, 128.8, 128.4, 128.1, 128.0, 125.9, 125.7, 123.5, 122.9, 101.0, 61.0, 45.2, 40.1, 14.1. ESI-MS: m/z 635.9 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₃H₂₁BrINNaO₄S: 635.9312; found: 635.9312.