Copper-Catalyzed Domino Addition–Cyclization Reaction between Terminal Alkynes, Carbon Disulfide, and Oxiranes

Abstract

Copper or silver salts promote a domino addition–cyclization reaction between terminal alkynes, carbon disulfide, and oxiranes in a regioselective manner to afford 1,4-oxathiane derivatives in good yield.

Keywords

1,4-oxathiane - oxirane - terminal alkyne - transition metal - multicomponent reaction

• References and Notes

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• 18 Typical Procedure for Preparation of 4 and 6 To a mixture of terminal alkyne (1.5–2.0 mmol), Cu(OAc)₂ (0.1–0.2 mmol), sodium ascorbate (0.2–0.3 mmol), and (i-Pr)₂NEt (1.5–2.0 mmol) in H₂O–t-BuOH (2:1, 3 mL) at 0 °C were added CS₂ (3 mmol) and the oxirane or aziridine (1.0 mmol). After 30 min the resulting brownish mixture was warmed to ambient temperature and stirred for 8–14 h. After completion of the reaction, the mixture was diluted with EtOAc (5 mL) and sat. NH₄Cl solution (5 mL) was added. The mixture was stirred for an additional 30 min and the organic layer separated. The aqueous layer was extracted with EtOAc (3 × 4 mL), and the combined organic layers were dried over MgSO₄, filtered, and concentrated in vacuo. The residue was purified by chromatography (silica gel; hexane–EtOAc, 3:1) to give the pure product.
• 19 N-Ts Aziridine 5 was prepared using the literature procedures.¹⁷ Representative Analytical Data 2-Benzylidene-6-methyl-1,4-oxathiane-3-thione (4a) Pale yellow oil; yield 0.19 g (79%). IR (KBr): ν_max = 3025, 2967, 1610, 1543, 1326, 1121 cm^–1. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.29 (3 H, d, ³ J = 7.0 Hz, Me), 3.30 (1 H, dd, ² J = 11.7 Hz, ³ J = 9.1 Hz, CH), 3.41 (1 H, dd, ² J = 11.7 Hz, ³ J = 5.6 Hz, CH), 4.58–4.64 (1 H, m, CH), 5.49 (1 H, s, CH), 7.18 (1 H, t, ³ J = 6.9 Hz), 7.26 (2 H, d, ³ J = 6.8 Hz), 7.31 (2 H, d, ³ J = 6.6 Hz). ¹³C NMR (125.7 MHz, CDCl₃): δ = 19.1 (Me), 42.8 (CH₂), 79.1 (CH), 102.2 (CH), 125.4 (2 CH), 129.2 (CH), 131.0 (2 CH), 136.3 (C), 156.7 (C), 213.9 (C). MS: m/z (%) = 236 (2) [M⁺], 160 (38), 119 (56), 105 (74), 77 (100), 58 (42). Anal. Calcd for C₁₂H₁₂OS₂ (236.35): C, 60.98; H, 5.12; S, 27.13. Found: C, 61. 15; H, 5.27; S, 27.19. 2-Benzylidene-6-ethyl-1,4-oxathiane-3-thione (4b) Pale yellow oil; yield 0.18 g (73%). IR (KBr): ν_max = 3021, 3010, 2945, 1634, 1536, 1325, 1130 cm^–1. ¹H NMR (500.1 MHz, CDCl₃): δ = 0.91 (3 H, t, ³ J = 6.2 Hz, Me), 1.56–1.60 (2 H, m, CH₂), 3.25–3.37 (2 H, m, CH₂), 4.61–4.66 (1 H, m, CH), 5.23 (1 H, s, CH), 7.14 (1 H, t, ³ J = 6.7 Hz), 7.24 (2 H, d, ³ J = 6.4 Hz), 7.31 (2 H, d, ³ J = 6.4 Hz). ¹³C NMR (125.7 MHz, CDCl₃): δ = 14.3 (Me), 24.7 (CH₂), 45.2 (CH₂), 80.7 (CH), 101.5 (CH), 124.3 (2 CH), 127.4 (CH), 130.0 (2 CH), 136.2 (C), 153.8 (C), 215.4 (C). MS: m/z (%) = 250 (7) [M⁺], 174 (47), 119 (61), 105 (78), 77 (100), 72 (58). Anal. Calcd for C₁₃H₁₄OS₂ (250.38): C, 62.36; H, 5.64; S, 25.61. Found: C, 62.56; H, 5.78; S, 25.69.