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

Leticia Minor-Villar; Rodolfo Tello-Aburto; Horacio F. Olivo; Aydee Fuentes; Moises Romero-Ortega

doi:10.1055/s-0032-1317525

Synlett, Table of Contents

Synlett 2012; 23(19): 2835-2839
DOI: 10.1055/s-0032-1317525

letter

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

Leticia Minor-Villar

^aDepartamento de Química Orgánica, Facultad de Química, Universidad Autónoma del Estado de México, Toluca, México Fax: +52(722)2173890 Email: mromeroo@uaemex.mx

,

Rodolfo Tello-Aburto

^bMedicinal and Natural Products Chemistry, The University of Iowa, Iowa City, IA 52242, USA

,

Horacio F. Olivo

^bMedicinal and Natural Products Chemistry, The University of Iowa, Iowa City, IA 52242, USA

,

Aydee Fuentes

^aDepartamento de Química Orgánica, Facultad de Química, Universidad Autónoma del Estado de México, Toluca, México Fax: +52(722)2173890 Email: mromeroo@uaemex.mx

,

Moises Romero-Ortega*

^aDepartamento de Química Orgánica, Facultad de Química, Universidad Autónoma del Estado de México, Toluca, México Fax: +52(722)2173890 Email: mromeroo@uaemex.mx

› Author Affiliations

Abstract

All articles of this category

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.

Full Text

References

References

1a Gnas Y, Glorius F. Synthesis 2006; 1899
1b Seyden-Penne J. Chiral Auxiliaries and Ligands in Asymmetric Synthesis. John Wiley & Sons; New York: 1995

2a Ager DJ, Prakash I, Schaad DR. Aldrichimica Acta 1997; 30: 3
2b Ager DJ, Prakash I, Schaad DR. Chem. Rev. 1996; 96: 835
2c Evans DA. Aldrichimica Acta 1982; 15: 23

3a Evans DA, Ellman JA. J. Am. Chem. Soc. 1989; 111: 1063
3b Velazquez F, Olivo HF. Curr. Org. Chem. 2002; 6: 303
3c Crimmins MT, Shamszad M. Org. Lett. 2007; 9: 149
3d Osorio-Lozada A, Olivo HF. Org. Lett. 2008; 10: 617

4a Ortiz A, Sansinenea E. J. Sulfur Chem. 2007; 28: 1
4b Yan TH, Hung AW, Lee HC, Chang CS, Liu WH. J. Org. Chem. 1995; 60: 3301
4c Guz NR, Phillips AJ. Org. Lett. 2002; 4: 2253

5a Evans DA, Bartroli J, Shih TL. J. Am. Chem. Soc. 1981; 103: 2127
5b Nerz-Stormnes M, Thornton ER. J. Org. Chem. 1991; 56: 2489

6a Nagao Y, Hagiwara Y, Kumagai T, Ochiai M, Inoue T, Hashimoto K, Fujita E. J. Org. Chem. 1986; 51: 2391
6b Nagao Y, Yamada S, Kumagai T, Ochiai M, Fujita E. J. Chem. Soc., Chem. Commun. 1985; 1418
6c Gonzalez A, Aiguade J, Urpi F, Vilarrasa J. Tetrahedron Lett. 1996; 37: 8949
6d Romero-Ortega M, Colby DA, Olivo HF. Tetrahedron Lett. 2002; 43: 6439

7 Mukhtar TA, Wright GD. Chem. Rev. 2005; 105: 529

8a Diekema DJ, Jones RN. Lancet 2001; 358: 1975
8b Jones RN, Moet GJ, Sader HS, Mendes RE, Castanhira M. J. Antimicrob. Chemother. 2009; 63: 716

9 Crimmins MT, King BW, Tabet EA. J. Am. Chem. Soc. 1997; 119: 7883
10 Crimmins MT, Chaudhary K. Org. Lett. 2000; 2: 775
11 Sabala R, Hernandez-Garcia L, Ortiz A, Romero M, Olivo HF. Org. Lett. 2010; 19: 4268

12a Palomo C, Oiarbide M, Dias F, Ortiz A, Linden A. J. Am. Chem. Soc. 2001; 123: 5602
12b Ortiz A, Quintero L, Hernandez H, Maldonado S, Mendoza G, Bernes S. Tetrahedron Lett. 2003; 44: 1129
12c Palomo C, Oiarbide M, Lopez R, Gonzalez PB, Gomez-Bengoa E, Sa JM, Linden A. J. Am. Chem. Soc. 2006; 128: 15236

13a Shibahara F, Suenami A, Yoshida A, Murai T. Chem. Commun. 2007; 2354
13b Mohammadpoor-Baltork I, Khodaei MM, Nikoofar K. Tetrahedron Lett. 2003; 44: 591
13c Kim YH, Chung BC, Chang S. Tetrahedron Lett. 1985; 26: 1079
13d Jorgensen KA, El-Wassimy MT. M, Lawesson SO. Tetrahedron 1983; 39: 469
13e Kochhar KS, Cottrell DA, Pinnick HW. Tetrahedron Lett. 1983; 24: 1323

14 Deng X, Chen N, Wang Z, Li X, Hu H, Xu J. Phosphorus, Sulfur Silicon 2011; 186: 1563

15a Sattigery VJ, Palle VP, Khera MK, Reddy R, Tiwari MK, Soni A, Abdul Rauf AR, Joseph S, Musib A, Dastidar SG, Srivastava PK. Int. Patent WO 2008023336, 2008 ; Chem. Abstr. 2008, 148, 308571.
15b Calo V, Nacci A, Volpe A. Gazz. Chim. Ital. 1997; 127: 283

16 Kitoh S.-I, Kubota A, Kunimoto K.-K, Kuwae A, Hanai K. J. Molec. Struct. 2005; 737: 277

17a Wilmore BH, Cassidy PB, Warters RL, Roberts JC. J. Med. Chem. 2001; 44: 2661
17b D’Amico JJ, Bollinger FG, Freeman JJ. J. Heterocycl. Chem. 1988; 25: 1503

18 White JD, Kawasaki M. J. Org. Chem. 1992; 57: 5292
19 Dickman DA, Meyers AI, Smith GA, Gawley RE. Org. Synth. 1985; 63: 136

20a Delaunay D, Toupet L, Le Corre M. J. Org. Chem. 1995; 60: 6604
20b Galvez E, Romea P, Urpi F. Org. Synth. 2009; 86: 70
20c Crimmins MT, Christie HS, Hughes CO. Org. Synth. 2011; 88: 364
20d Morales-Nava R, Fernandez-Zertuche M, Ordonez M. Molecules 2011; 16: 8803

21 Wu Y, Yang YQ, Hu Q. J. Org. Chem. 2004; 69: 3990
22 Kappe CO. Angew. Chem. Int. Ed. 2004; 43: 6250
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.