Synthesis of N-Benzothiazol-2-yl-amides by an Iron-Catalyzed Oxidative C(sp²)–H Functionalization

Abstract

Catalytic synthesis of N-benzothiazol-2-yl-amides from 1-acyl-3-(phenyl)thioureas was achieved in the presence of an iron catalyst through C(sp²)–H functionalization and C–S bond formation. Various N-benzothiazol-2-yl-amides were selectively obtained in good yields.

Key words

benzothiazole - iron catalysis - 1-acetyl-3-phenyl­thiourea - potassium persulfate - iron(III) chloride

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• 11 General Procedure A round-bottom flask equipped with a stir bar was charged with FeCl₃ (16.6 mg, 0.02 mmol), substituted 1-acetyl-3-(phenyl)thiourea (2 mmol) and Na₂S₂O₈ (245.0 mg, 2.0 mmol). DMSO (5 mL) was added to the reaction flask. The mixture was stirred at 100 °C for 1 h. After cooling to r.t., the reaction mixture was quenched with H₂O and extracted with EtOAc (2 × 20 mL). The organic layers were combined, dried over Na₂SO₄, concentrated under reduced pressure, and then purified by silica gel chromatography (acetone–PE, 1:4) to yield the desired product. N-{Naphtho[1,2-d]thiazol-2-yl}acetamide (2i) A green solid (80% yield); mp 309–310 °C. IR: ν = 3167.4, 3047.5, 2997.3, 2359.9, 1559.0 cm^–1. ¹H NMR (400 MHz, DMSO): δ = 12.57 (s, 1 H), 8.51 (dd, J = 8.2, 0.6 Hz, 1 H), 8.05 (dd, J = 8.3, 5.0 Hz, 2 H), 7.82 (d, J = 8.6 Hz, 1 H), 7.63 (dddd, J = 29.3, 8.2, 6.9, 1.3 Hz, 2 H), 2.25 (s, 3 H). ¹³C NMR (100 MHz, DMSO): δ = 169.70 (s), 158.46 (s), 144.74 (s), 132.26 (s), 128.75 (s), 127.58 (s), 127.31 (s), 127.01 (s), 126.23 (s), 124.18 (s), 123.16 (s), 120.02 (s), 23.16 (s). HRMS: m/z calcd for C₁₃H₁₀N₂OS [M]⁺: 242.0514; found: 242.0519. N-{6-Methoxybenzo[d]thiazol-2-yl}cyclopentane-carboxamide (2j) A brown solid (80% yield); mp 172–175 °C. IR: ν = 3178.3, 3066.2, 2930.6, 2360.0, 1605.9 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 10.88 (s, 1 H), 7.66 (d, J = 8.9 Hz, 1 H), 7.32 (d, J = 2.5 Hz, 1 H), 7.05 (dd, J = 8.9, 2.6 Hz, 1 H), 3.89 (s, 3 H), 2.33 (tt, J = 11.7, 3.5 Hz, 1 H), 1.94–1.82 (m, 2 H), 1.79–1.69 (m, 2 H), 1.66–1.47 (m, 3 H), 1.22–1.00 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 174.71 (s), 157.66 (s), 156.83 (s), 142.01 (s), 133.26 (s), 121.02 (s), 115.32 (s), 104.33 (s), 55.86 (s), 44.99 (s), 29.23 (s), 25.34 (s). HRMS: m/z calcd for C₁₅H₁₈N₂O₂S [M + H]⁺: 291.1167; found: 291.1172.