Carbonylative Synthesis of Thiochromenones via Palladium-Catalyzed tert-Butyl Isocyanide Insertion

Abstract

A flexible and efficient carbonylative synthesis of thiochromenones from the commercially available materials by utilizing tert-butyl isocyanide as carbonyl source has been developed. This methodology efficiently constructs thiochromenones in moderate to excellent yields with the advantages of wide range of substrates and being applicable to library synthesis.

Key words

thiochromenones - isocyanide - palladium-catalyzed - ­carbonylative - sulfide

• References and Notes

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• 23 General Procedure In a 15 mL sealed tube equipped with a magnetic stirring bar were added 1 (1 mmol), 2 (0.8 mmol), tert-butyl isocyanide (1.2 mmol, 136 μL), Pd(OAc)₂ (0.03 mmol, 7 mg), DPEPhos (0.06 mmol, 32 mg), Cs₂CO₃ (0.8 mmol, 261 mg), and anhydrous DMF (2.0 mL). The tube was purged with argon, and the contents were stirred at 100 °C for 2 h. Then Na₂S·9H₂O (1.2 mmol, 240 mg) was added for 2 h. After reaction completion, the mixture was filtered through a pad of Celite, and DMF was removed by a vacuum. The combined filtrates were refluxed in THF (15 mL) and oxalic acid (1 M, 3 mL) for 8 h. The solvents were removed under reduced pressure, then poured into brine (20 mL) and extracted by ethyl acetate (3 × 30 mL). The combined organic layers were dried (Na₂SO₄) and evaporated. The residue was purified on a silica gel column using petroleum ether/ethyl acetate as the eluent to give the pure target product.
• 24 2-(2-Fluorophenyl)-4H-thiochromen-4-one (3j) Yellow solid (116 mg, 57%); mp 128–130 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.56 (d, J = 7.9 Hz, 1 H), 7.65 (d, J = 3.1 Hz, 2 H), 7.56 (dd, J = 13.0, 5.6 Hz, 2 H), 7.48 (dd, J = 13.2, 7.1 Hz, 1 H), 7.29 (d, J = 7.5 Hz, 1 H), 7.21 (d, J = 12.4 Hz, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 180.6 (s), 160.6 (s), 158.1 (s), 147.1 (s), 138.2 (s), 132.2 (d, J _C-F = 8.4 Hz), 131.8 (s), 131.0 (s), 130.3 (d, J _C-F = 1.9 Hz), 128.8 (s), 128.0 (s), 127.0 (d, J _C-F = 3.7 Hz), 126.5 (s), 124.9 (d, J _C-F = 3.8 Hz), 124.6 (d, J _C-F = 13.1 Hz), 117.0 (s), 116.8 (s). IR (KBr): 1627, 1593, 1439, 1325, 1098, 758, 732, 685 cm^–1. HRMS: m/z calcd for C₁₅H₁₀FOS [M + H]⁺: 257.0437; found: 257.0428.
• 25 2-(Thiophen-3-yl)-4H-thiochromen-4-one (3n) Yellow solid (78 mg, 40%); mp 135–140 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.53 (d, J = 8.0 Hz, 1 H), 7.78 (s, 1 H), 7.65–7.43 (m, 6 H). ¹³C NMR (101 MHz, CDCl₃): δ = 181.2 (s), 147.0 (s), 137.8 (s), 137.3 (s), 131.8 (s), 131.2 (s), 128.7 (s), 127.9 (s), 127.7 (s), 126.5 (s), 125.4 (s), 125.2 (s), 122.2 (s). IR (KBr): 3094, 1605, 1582, 1543, 1329, 1101, 774, 738, 631 cm^–1. HRMS: m/z calcd for C₁₃H₉OS₂ [M + H]⁺: 245.0096; found: 245.0093.
• 26 8-Fluoro-2-(p-tolyl)-4H-thiochromen-4-one (5a) Yellow solid (143 mg, 66%); mp 160–164 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.35 (d, J = 8.0 Hz, 1 H), 7.62 (d, J = 8.0 Hz, 2 H), 7.52 (dd, J = 13.4, 7.9 Hz, 1 H), 7.39 (t, J = 8.7 Hz, 1 H), 7.32 (d, J = 7.8 Hz, 2 H), 7.24 (s, 1 H), 2.44 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 180.2 (s), 159.3 (s), 156.8 (s), 152.2 (s), 141.8 (s), 133.8 (s), 132.7 (s), 132.6 (s), 130.2 (s), 127.9 (d, J _C-F = 7.8 Hz), 127.0 (s), 124.3 (s), 123.0 (s), 117.2 (d, J _C-F = 19.6 Hz), 21.5 (s). IR (KBr): 2922, 1620, 1601, 1549, 1247, 1129, 819 798, 709 cm^–1. HRMS: m/z calcd for C₁₆H₁₂FOS [M + H]⁺: 271.0594; found: 271.0598.
• 27 N-(tert-Butyl)-1-(2-fluorophenyl)-3-phenylprop-2-yn-1-imine (8) Yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.67 (t, J = 8.6 Hz, 1 H), 7.53 (d, J = 7.8 Hz, 2 H), 7.43–7.33 (m, 4 H), 7.17 (t, J = 7.5 Hz, 1 H), 7.13–7.05 (m, 1 H), 1.58 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃): δ = 161.9 (s), 159.4 (s), 144.6 (s), 133.4 (s), 131.8 (s), 131.0 (d, J _C-F = 8.4 Hz), 130.4 (d, J _C-F = 2.4 Hz), 129.8 (s), 129.4 (d, J _C-F = 11.0 Hz), 128.7 (s), 124.2 (d, J _C-F = 3.7 Hz), 122.0 (s), 116.5 (s), 116.3 (s), 98.9 (d, J _C-F = 2.9 Hz), 85.0 (s), 57.9 (s), 29.6 (s). IR (KBr): 2968, 1609, 1590, 1485, 1305, 1222, 752, 648. HRMS: m/z calcd for C₁₉H₁₈FN [M + H]⁺: 280.1502; found: 280.1509.