Epoxides to α-Mercapto-γ-lactones via Ionic Liquid Promoted Mercaptoacetylative Ring-Opening-Ring-Closing Cascade

Abstract

Task-specific ionic liquid promoted {[Bmim]OH} one-pot synthesis of α-mercapto-γ-lactones is reported. The present protocol involves regioselective epoxide ring opening and intramolecular translactonisation cascade. A variety of epoxides undergo this ring-opening-ring-closing cascade with 2-methyl-2-phenyl-1,3-­oxathiolan-5-one to afford α-mercapto-γ-lactones diastereoselectively in good to excellent yields. After isolation of the product, the ionic liquid [Bmim]OH could be easily recovered and reused without any loss of efficiency.

γ-lactones - epoxides - ionic liquids - cascade reactions - translactonization - stereoselective synthesis

References and Notes

1a Koch SSC. Chamberlin AR. In Studies in Natural Products Chemistry   Vol. 16:  . Elsevier; Amsterdam: 1995.  p.687-725  

1b Friedrichsen W. In Comprehensive Heterocyclic Chemistry II   Vol. 2:  Bird CW. Pergamon Press; Oxford: 1996.  p.351 

1c Rao YS. Chem. Rev.  1976,  76:  625 

1d Haffmann HMR. Rabe J. Angew. Chem., Int. Ed. Engl.  1985,  24:  94 

1e Mulzer J. Salimi N. Hartl H. Tetrahedron: Asymmetry  1993,  4:  457 

1f Schmitz WD. Messerschmidt NB. Romo D. J. Org. Chem.  1998,  63:  2058 

1g Maier MS. Marimon DIG. Stortz C.-A. Alder MJ. J. Nat. Prod.  1999,  62:  1565 

1h Hislop J.-A. Hunt MB. Fielder S. Rowan DD. J. Agric. Food Chem.  2004,  52:  7075 

1i Frediani P. Rosi L. Frediani M. Bartolucci C. Bambagiotti-Alberti M. J. Agric. Food Chem.  2007,  55:  3877 

1j Schlutt B. Moran N. Schieberle P. Hofmann T. J. Agric. Food Chem.  2007,  55:  9634 

1k Pertino MW. Theoduloz C. Rodriguez JA. Yanez T. Lazo V. Schmeda-Hirschmann G. J. Nat. Prod.  2010,  73:  639 

2 Lambert JD. Rice JE. Hong J. Hou Z. Yang CS. Bioorg. Med. Chem. Lett.  2005,  15:  873 

3a Harchen C. Bruchner R. Angew. Chem. Int. Ed.  1997,  36:  2750 

3b Drioli S. Felluga F. Forzato C. Nitti P. Pitacco G. Valentin E. J. Org. Chem.  1998,  63:  2385 

3c de March P. Figueredo M. Font J. Raya J. Org. Lett.  2000,  2:  163 

3d Delhaye L. Merschaert A. Diker K. Houpis IN. Synthesis  2006,  1437 

4a Gutierrez JLG. Jimenez-Cruz F. Espinosa NR. Tetrahedron Lett.  2005,  46:  803 

4b Burstein C. Tschan S. Xie X. Glorius F. Synthesis  2006,  2418 

4c Tiecco M. Testaferri L. Temperini A. Terlizzi R. Bagnoli L. Marini F. Santi C. Synlett  2006,  587 

4d Vitale M. Prestat G. Lopes D. Madec D. Poli G. Synlett  2006,  2231 

4e Cho CS. Shim HS. Tetrahedron Lett.  2006,  47:  3835 

4f Li Z. Gao Y. Jiao Z. Wu N. Wang DZ. Yang Z. Org. Lett.  2008,  10:  5163 

4g Park HS. Kwon DW. Lee K. Kim YH. Tetrahedron Lett.  2008,  49:  1616 

4h Antoniotti S. Dunach E. Tetrahedron Lett.  2009,  50:  2536 

4i Gooßen LJ. Ohlmann DM. Dierker M. Green Chem.  2010,  12:  197 

4j Dias LC. de Castro IBD. Steil LJ. Augusto T. Tetrahedron Lett.  2006,  47:  213 

4k Olejniczak T. Mironowicz A. Wawrzenczyk C. Bioorg. Chem.  2003,  31:  199 

5a Tietze LF. Beifuss U. Angew. Chem., Int. Ed. Engl.  1993,  32:  131 

5b Enders D. Grndal C. Huttl MRM. Angew. Chem. Int. Ed.  2007,  46:  1570 

5c Nicolaou KC. Chen JS. Chem. Soc. Rev.  2009,  38:  2993 

5d Morten CJ. Byers JA. Van Dyke AR. Vilotijevic I. Jamison TF. Chem. Soc. Rev.  2009,  38:  3175 

6a Domino Reactions in Organic Synthesis   Tietze LF. Brasche G. Gericke KM. Wiley-VCH; Weinheim: 2006. 

6b Fustero S. Jimenez D. Sanchez-Rosello M. del Pozo C. J. Am. Chem. Soc.  2007,  129:  6700 

6c Bi H.-P. Liu X.-Y. Gou F.-R. Guo L.-N. Duan X.-H. Shu X.-Z. Liang Y.-M. Angew. Chem. Int. Ed.  2007,  46:  7068 

6d Rolfe A. Young K. Hanson PR. Eur. J. Org. Chem.  2008,  31:  5254 

7a Kozytska MV. Dudley GB. Chem. Commun.  2005,  3047 

7b Bontemps S. Gornitzka H. Bouhadir G. Miqueu K. Bourissou D. Angew. Chem. Int. Ed.  2006,  45:  1611 

7c Bontemps S. Bouhadir G. Miqueu K. Bourissou D. J. Am. Chem. Soc.  2006,  128:  12056 

7d Tejedor D. Mendez-Abt G. Gonzalez-Platas J. Ramirez MA. Garca-Tellado F. Chem. Commun.  2009,  2368 

8a Nakamura H. Shim J.-G. Yamamoto Y. J. Am. Chem. Soc.  1997,  119:  8113 

8b Nakamura H. Aoyagi K. Shim J.-G. Yamamoto Y. J. Am. Chem. Soc.  2001,  123:  372 

8c Hili R. Yudin AK. Angew. Chem. Int. Ed.  2008,  47:  4188 

8d Baktharaman S. Hili R. Yudin AK. Aldrichimica Acta  2008,  41:  109 

8e Kimura M. Tamaki T. Nakata M. Tohyama K. Tamaru Y. Angew. Chem. Int. Ed.  2008,  120:  5887 

8f Hili R. Yudin AK. J. Am. Chem. Soc.  2009,  131:  16404 

9a Corey EJ. Russey WE. Ortiz de Montellano PR.
J. Am. Chem. Soc.  1966,  88:  4750 

9b van Tamelen EE. Willett JD. Clayton RB. Lord KE. J. Am. Chem. Soc.  1966,  88:  4752 

9c Neighbors JD. Beutler JA. Wiemer DF. J. Org. Chem.  2005,  70:  925 

9d Vilotijevic I. Jamison TF. Angew. Chem. Int. Ed.  2009,  48:  5250 

9e Topczewski JJ. Callahan MP. Neighbors JD. Wiemer DF. J. Am. Chem. Soc.  2009,  131:  14630 

10a Samuel S.-MC. Gordon WK. J. Chem. Soc., Perkin Trans. 1  1991,  3225 

10b Ravelo JL. Radriguez CM. Martin VS. J. Organomet. Chem.  2006,  691:  5326 

11a Chowdhury S. Mohan RS. Scott JL. Tetrahedron  2007,  63:  2363 

11b Martins MAP. Frizzo CP. Moreira DN. Zanatta N. Bonacorso HG. Chem. Rev.  2008,  108:  2015 

11c Prechtl MHG. Scholten JD. Nuto BAD. Dupont J. Curr. Org. Chem.  2009,  13:  1705 

11d Sureshkumar M. Lee C.-K. J. Mol. Catal. B: Enzym.  2009,  60:  1 

11e Olivier-Bourbigou H. Magna L. Morvan D. Appl. Catal., A  2010,  373:  1 

11f Giernoth R. Angew. Chem. Int. Ed.  2010,  49:  2834 

12a Ionic Liquids in Synthesis   Wasserscheid P. Welton T. Wiley-VCH; Weinheim: 2008. 

12b Calo V. Nacci A. Monopoli A. Cotugno P. Angew. Chem. Int. Ed.  2009,  48:  6101 

12c Gong K. Wang H.-L. Luo J. Liu Z.-L. J. Heterocycl. Chem.  2009,  46:  1145 

12d Yavari I. Kowsari E. Mol. Diversity  2009,  13:  519 

12e Yadav LDS. . Srivastava VP. Tetrahedron Lett.  2010,  51:  739 

13a Yadav LDS. Patel R. Rai VK. Srivastava VP. Tetrahedron Lett.  2007,  48:  7793 

13b Yadav LDS. Patel R. Srivastava VP. Synlett  2008,  583 

13c Yadav LDS. Singh S. Rai VK. Tetrahedron Lett.  2009,  50:  2208 

13d Yadav LDS. Singh S. Rai VK. Green Chem.  2009,  11:  878 

13e Yadav LDS. Kapoor R. . Synlett  2009,  1055 

13f Yadav LDS. Rai VK. Singh S. Singh P. Tetrahedron Lett.  2010,  51:  1662 

14 Yadav LDS. Yadav S. Rai VK. Tetrahedron  2005,  61:  10013 

15

General Procedure for the Synthesis of α-Mercapto-γ-lactones 4
To a stirred solution of 2-methyl-2-phenyl-1,3-oxathiolan-5-one (2, 1 mmol) in [Bmim]OH-H₂O (0.5-1 mL, 4:1), epoxide 1 (1 mmol) was added dropwise and stirred at r.t. for 30 min, then the reaction mixture was stirred at 50 ˚C for 6-15 h (Table  [¹] ). After completion of reaction (monitored by TLC), the reaction mixture was cooled to r.t., diluted with H₂O (5 mL), and extracted with EtOAc (3 × 5 mL), dried over anhyd Na₂SO₄, filtered, and evaporated to dryness.
A mixture of the crude product 4 and acetophenone thus obtained was subjected to silica gel column chromatography using EtOAc-n-hexane as eluent to afford an analytically pure sample of 4 and acetophenone, which was recycled to 2.^¹4 After isolation of the product, the remaining aqueous layer containing the ionic liquid was washed with Et₂O (2 × 5 mL) to remove any organic impurity, dried under vacuum at 90 ˚C to afford [Bmim]OH, which was used in subsequent runs without further purification.
Physical Data of Representative CompoundsCompound 4a ( cis / trans = 60:40) cis: IR (film): ν_max = 2995, 2876, 2554, 1765, 1607, 1583, 1455 cm^-¹. ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 2.25 (1 H, m), 2.39 (1 H, ddd, J = 13.2, 6.8, 6.7 Hz), 3.85 (1 H, dd, J = 7.7, 6.7 Hz), 5.28 (1 H, dd, J = 6.9, 6.8 Hz), 7.21-7.32 (m, 5 H_arom). ^¹³C NMR (100 MHz, CDCl₃-TMS): δ = 41.1, 46.2, 80.1, 127.1, 128.8, 129.1, 140.1, 178.4. MS (EI): m/z = 194 [M⁺]. Anal. Calcd for C₁₀H₁₀O₂S: C, 61.83; H, 5.19. Found: C, 62.2; H, 5.02.
trans: IR (film): ν_max = 2993, 2876, 2558, 1767, 1609, 1582, 1453 cm^-¹. ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 2.20 (1 H, m), 2.46 (1 H, ddd, J = 13.2, 6.8, 6.9 Hz), 3.88 (1 H, dd, J = 7.4, 6.9 Hz), 5.05 (1 H, dd, J = 10.3, 6.8 Hz), 7.23-7.36 (m, 5H_arom).
Compound 4c ( cis / trans = 67:33)
cis: IR (film): ν_max = 2998, 2875, 2554, 1768, 1605, 1585, 1456 cm^-¹. ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 2.25 (1 H, m), 2.39 (1 H, ddd, J = 13.2, 6.8, 6.7 Hz), 3.83 (1 H, dd, J = 7.7, 6.7 Hz), 5.29 (1 H, dd, J = 6.9, 6.8 Hz), 7.21-7.34 (m, 2 H_arom,), 7.58-7.61 (m, 2 H_arom). ^¹³C NMR (100 MHz, CDCl₃-TMS): δ = 41.6, 46.9, 81.1, 129.6, 130.2, 132.3, 143.5, 178.5. MS (EI): m/z = 228 [M⁺], 230 [M + 2⁺]. Anal. Calcd for C₁₀H₉ClO₂S: C, 52.52; H, 3.97. Found: C, 52.15; H, 4.29.
trans: IR (film): ν_max = 3001, 2876, 2552, 1770, 1609, 1580, 1457 cm^-¹. ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 2.20 (1 H, m), 2.46 (1 H, ddd, J = 13.2, 6.8, 6.9 Hz), 3.86 (1 H, dd, J = 7.4, 6.9 Hz), 5.07 (1 H, dd, J = 10.3, 6.8 Hz), 7.23-7.36 (m, 2 H_arom), 7.57-7.62 (m, 2 H_arom).

16

Isolation of 3a and 3c and their Conversion into the Corresponding α-Mercapto-γ-lactones 4a and 4c
The procedure followed was the same as described above for the synthesis of 4 except that the stirring time in this case was only 25-30 min at r.t. Purified by silica gel chromatography using EtOAc-n-hexane as eluent to afford an analytically pure sample of 3a and 3c. Finally, the intermediate alcohols 3a and 3c (1 mmol) were quantitatively converted into the corresponding γ-lactones 4a and 4b by stirring at 50 ˚C in [Bmim]OH-H₂O (4:1) for 6.5 h.
Physical Data of Intermediate Alcohols 3a and 3cCompound 3a (Diastereomeric Mixture = 60:40)
Major: IR (film): ν_max = 3435, 2965, 2878, 1775, 1605, 1581, 1456 cm^-¹. ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 1.18 (3 H, s), 2.13-2.17 (2 H, m), 3.99 (1 H, dd, J = 12.0, 7.8 Hz), 4.91 (1 H, dd, J = 7.6, 5.7 Hz), 7.21-7.36 (m, 10H_arom). ^¹³C NMR (100 MHz; CDCl₃-TMS): δ = 20.8, 37.2, 44.7, 77.2, 98.7, 127.1, 127.8, 128.4, 128.8, 129.1, 129.5, 139.8, 141.1, 177.2. MS (EI): m/z = 314 [M⁺]. Anal. Calcd for C₁₈H₁₈O₃S: C, 68.76; H, 5.77. Found: C, 68.98; H, 5.40.
Minor: ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 1.19 (3 H, s), 2.15-2.20 (2 H, m), 3.89 (1 H, t, J = 2.2 Hz), 4.98 (1 H, dd, J = 7.8, 5.7 Hz), 7.21-7.34 (m, 10 H_arom).
Compound 3c (Diasteriomeric Mixture = 67:33)
Major: IR (film): ν_max = 3440, 2985, 2876, 1772, 1607, 1584, 1457 cm^-¹. ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 1.21 (3 H, s), 2.16-2.20 (2 H, m), 3.92 (1 H, dd, J = 12.1, 7.8 Hz), 4.95 (1 H, dd, J = 7.5, 5.7 Hz), 7.21-7.52 (m, 7 H_arom), 7.70-7.90 (m, 2 H_arom). ^¹³C NMR (100 MHz, CDCl₃-TMS): δ = 21.7, 37.4, 44.9, 77.3, 98.6, 127.7, 128.9, 129.2, 129.8, 130.1, 132.2, 139.7, 142.5, 177.3. MS (EI): m/z = 348 [M⁺], 350 [M + 2⁺]. Anal. Calcd for C₁₈H₁₇ClO₃S: C, 61.97; H, 4.91. Found: C, 62.20; H, 5.28.
Minor: ^¹H NMR (400 MHz, CDCl₃-D₂O-TMS): δ = 1.19 (3 H, s), 2.17-2.22 (2 H, m), 3.89 (1 H, t, J = 2.3 Hz), 4.98 (1 H, dd, J = 7.8, 5.6 Hz), 7.22-7.54 (m, 7 H_arom), 7.72 (m, 2 H_arom).

17 Brace NO. J. Fluorine Chem.  2003,  123:  237