Desulfurization–Oxygenation of Chiral 1,3-Thiazolidine-2-thiones and 1,3-Oxazolidine-2-thiones Using Propylene Oxide and Microwave Irradiation

Abstract

An efficient method for the desulfurization–oxygenation of 1,3-thiazolidine-2-thiones and 1,3-oxazolidine-2-thiones using propylene oxide and employing microwave irradiation is described. This strategy of oxygenation of the thiocarbonyl group provides an attractive methodology to prepare chiral 1,3-thiazolidin-2-ones and 1,3-oxazolidin-2-ones from the corresponding precursors in good yields.

Key words

thiazolidinethiones - oxazolidinethiones - thiazolidinones - propylene oxide - chiral auxiliaries.

• References

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• 23 General Procedure for the Synthesis of 1,3-Thiazolidin-2-ones 4 and 1,3-Oxazolidin-2-ones 1 under Thermal Conditions: A solution of thiazolidine-2-thione 2 or oxazolidine-2-thione 3 (1.0 mmol) in propylene oxide (2.5 mL) was heated in a sealed tube at 100 °C under nitrogen during 48 h. The reaction mixture was then allowed to cool to r.t. and the solvent was evaporated under reduced pressure. The residue was purified by silica gel flash column chromatography eluting with hexanes–EtOAc (4:1) for the 1,3-thiazolidin-2-ones and hexanes–EtOAc (3:2) for the 1,3-oxazolidin-2-ones to give analytically pure products 4 and 1. General Procedure for the Synthesis of 1,3-Thiazolidin-2-ones 4 and 1,3-Oxazolidin-2-ones 1 using Microwave Irradiation: To a solution of thiazolidine-2-thione 2 or oxazolidine-2-thione 3 (1.0 mmol) in CHCl₃ (1.5 mL) was added propylene oxide (1.5 mL) in a 10-mL vessel with a screw cap under a nitrogen blanket. The reaction mixture was heated at 150 °C (hold time 60 min, ramp time 1–2 min). After cooling (cool down, 50 °C, 2 min), the reaction mixture was allowed to cool to r.t. and the solvent was removed under reduced pressure. The residue was purified by silica gel flash column chromatography eluting with hexanes–EtOAc (4:1) for 1,3-thiazolidin-2-ones and hexanes–EtOAc (3:2) for 1,3-oxazolidin-2-ones to give analytically pure products 4 and 1, respectively. (4S)-Isopropyl-1,3-thiazolidin-2-one (4a): was obtained as a white solid after purification by flash column chromatography; mp 75–76 °C (CH₂Cl₂–hexanes); [α]²⁴ _D +19.2 (c = 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 6.96 (br, 1 H), 3.60–3.68 (dt, J = 7.8, 15.3 Hz, 1 H), 3.35 (dd, J = 7.5, 10.9 Hz, 1 H), 3.16 (dd, J = 8.2, 10.9 Hz, 1 H), 1.77–1.89 (m, 1 H), 1.01 (d, J = 6.7 Hz, 3 H), 0.96 (d, J = 6.7 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 175.8, 61.4, 32.5, 32.4, 18.7, 18.1. HRMS: m/z calcd for C₆H₁₁NOS: 145.0556; found: 145.0562. (4S)-4-Benzyl-1,3-thiazolidin-2-one (4b): was obtained as a white solid after purification by flash column chromatography; mp 69–70 °C (CH₂Cl₂–hexanes); [α]²⁵ _D –9.6 (c = 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 7.23–7.36 (m, 3 H), 7.16–7.20 (m, 2 H), 6.01 (br, 1 H), 4.07 (m, 1 H), 3.43 (dd, J = 7.2, 11.1 Hz, 1 H), 3.17 (dd, J = 6.3, 11.1 Hz, 1 H), 2.93 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 174.8, 136.4, 129.0, 128.9, 127.1, 56.5, 40.9, 34.3. HRMS: m/z calcd for C₁₀H₁₁NOS: 193.0556; found: 193.0555. (4R)-Phenyl-1,3-thiazolidin-2-one (4c): was obtained as a white solid after purification by flash column chromatography; mp 162–164 °C (CH₂Cl₂–hexanes); [α]²⁴ _D –86.4 (c = 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 7.61 (br, 1 H), 7.32–7.39 (m, 5 H), 4.94 (td, J = 0.9, 7.5 Hz, 1 H), 3.68 (dd, J = 7.5, 11.0 Hz, 1 H), 3.26 (dd, J = 7.7, 11.0 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 174.2, 139.9, 128.3, 127.8, 125.5, 58.4, 37.0. HRMS: m/z calcd for C₉H₉NOS: 179.0399; found: 179.0390. (4R)-Methyl-1,3-thiazolidin-2-one (4d): was obtained as a white solid after purification by flash column chromatography; mp 40–42 °C (CH₂Cl₂–hexanes); [α]²⁴ _D +12.80 (c = 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 6.70 (br, 1 H), 3.99–4.06 (m, 1 H), 3.47 (dd, J = 7.2, 10.8 Hz, 1 H), 3.04 (dd, J = 7.2, 10.8 Hz, 1 H), 1.34 (d, J = 6.2 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 175.4, 51.2, 36.5, 20.5. (4R,5S)-Indano[1,2-d]-1,3-thiazolidine-2-one (4e): was obtained as a white solid after purification by flash column chromatography; mp 195–196 °C (CH₂Cl₂–hexanes); [α]²³ _D +3.2 (c = 0.5 CHCl₃). ¹H NMR (500 MHz, CDCl₃–DMSO): δ = 8.21 (br, 1 H), 7.37–7.39 (m, 1 H), 7.24–7.31 (m, 3 H), 5.17 (d, J = 7.5 Hz, 1 H), 4.67 (td, J = 3.0, 7.5 Hz, 1 H), 3.48 (dd, J = 7.5, 17.0 Hz, 1 H), 3.20 (dd, J = 3.0, 17.0 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃–DMSO): δ = 173.1, 140.3, 139.4, 128.2, 126.9, 124.5, 124.3, 63.0, 46.7. HRMS: m/z calcd for C₁₀H₉NOS: 191.0399; found: 191.0393.