Regio- and Enantioselective Ring-Opening of Epoxides with HMDST: A Straightforward Access to 1,2-Mercaptoalcohols

Abstract

TBAF-catalyzed reaction of a range of substituted ­epoxides with hexamethyldisilathiane smoothly affords a direct and simple access to β-mercaptoalcohols in a highly regio- and stereoselective way.

Key words

epoxides - thiosilane - 1,2-mercaptoalcohols - enantio­selectivity - regioselectivity

References

• Inter alia:
• 1a Lidy W. Sundermeyer W. Tetrahedron Lett.  1973,  1449 
• 1b Mullis JC. Weber WP. J. Org. Chem.  1982,  47:  2873 
• 1c Guddenheim TL. J. Am. Chem. Soc.  1982,  104:  5849 
• 1d Gassman PG. Gremban RS. Tetrahedron Lett.  1984,  25:  3259 
• 1e Behrens CH. Sharpless KB. J. Org. Chem.  1985,  50:  5696 
• 1f Yamashita H. Bull. Chem. Soc. Jpn.  1988,  61:  1213 
• 1g Iqbal J. Pandey A. Shukla A. Srivastava RR. Tripathi S. Tetrahedron  1990,  46:  6423 ; and references cited therein
• 1h Kesavan V. Bonnet-Delpon D. Bégué J.-P. Tetrahedron Lett.  2000,  41:  2895 ; and references cited therein
• Inter alia:
• 2a Lalancette JM. Frêche A. Can. J. Chem.  1971,  49:  4047 
• 2b Vougioukas AE. Kagan HB. Tetrahedron Lett.  1987,  28:  6065 
• 2c Nishikubo T. Iizawa T. Shimojo M. Kato T. Shiina A. J. Org. Chem.  1990,  55:  2536 
• 2d Chini M. Crotti P. Giovani E. Macchia F. Pineschi M. Synlett  1992,  303 
• 2e Albanese D. Landini D. Penso M. Synthesis  1994,  34 
• 2f Chou W.-C. Chen L. Fang J.-M. Wong C.-H. J. Am. Chem. Soc.  1994,  116:  6191 
• 2g Iida T. Yamamoto Y. Sasai H. Shibasaki M. J. Am. Chem. Soc.  1997,  119:  4783 
• 2h Wu MH. Jacobsen EN. J. Org. Chem.  1998,  63:  5252 
• 2i Wu J. Hou X.-L. Dai L.-X. Xia L.-J. Tang M.-H. Tetrahedron: Asymmetry  1998,  9:  3431 
• 2j Yadav JS. Reddy BV. Baishya G. Chem. Lett.  2002,  906 
• 2k Friguelli F. Pizzo F. Tortoioli S. Vaccaro L. Tetrahedron Lett.  2003,  44:  6785 
• 2l Movassagh B. Sobhani S. Kheirdoush F. Fadaei Z. Synth. Commun.  2003,  33:  3103 
• 2m Heimgartner H. Fu C. Blagoev M. Linden A. Phosphorus, Sulfur Silicon Relat. Elem.  2005,  180:  1309 
• 3a Luly JR. Yi N. Soderquist J. Stein H. Cohen J. Perun TJ. Plattner JJ. J. Med. Chem.  1987,  30:  1609 
• 3b Meffre P. Vo Quang L. Vo Quang Y. Le Goffic F. Tetrahedron Lett.  1990,  31:  2291 
• 3c Scholz D. Billich A. Charpiot B. Ettmayer P. Lehr P. Roaenwirth B. Schreiner E. Gstach H. J. Med. Chem.  1994,  37:  3079 
• 3d Paulvannan K. Chen T. Synlett  1999,  1371 
• 3e Mühlman A. Classon B. Hallberg A. Samuelsson B. J. Med. Chem.  2001,  44:  3402 
• 4a Corey EJ. Clark DA. Goto G. Marfat A. Mioskowski C. Samuelsson B. Hammarstrom S. J. Am. Chem. Soc.  1980,  102:  1436 
• 4b Corey EJ. Clark DA. Goto G. Marfat A. Mioskowski C. Samuelsson B. Hammarstrom S. J. Am. Chem. Soc.  1980,  102:  3663 
• 4c Rokach J. Girard Y. Guindon Y. Atkinson JG. Larue M. Young RN. Masson P. Holme G. Tetrahedron Lett.  1980,  21:  1485 
• 5 Guindon Y. Young RN. Frenette R. Synth. Commun.  1981,  11:  391 
• 6 Caron M. Sharpless KB. J. Org. Chem.  1985,  50:  1560 
• 7 Guivisdalsky PN. Bittman R. J. Am. Chem. Soc.  1989,  111:  3077 
• 8 Hashiyama T. Inoue H. Takeda M. Aoe K. Kotera K. Konda M. J. Chem. Soc., Perkin Trans. 1  1985,  421 
• 9 Posner GH. Rogers DZ. J. Am. Chem. Soc.  1977,  79:  8208 
• 10a Iizawa T. Goto A. Nishikubo T. Bull. Chem. Soc. Jpn.  1989,  62:  597 
• 10b Tanabe Y. Mori K. Yoshida Y. J. Chem. Soc., Perkin Trans. 1  1997,  671 
• 10c Pirrung MC. Tumey LN. Raetz CR. Jackman JE. Snahalatha K. McClerren AL. Fierke CA. Gantt SL. Rusche KM. J. Med. Chem.  2002,  45:  4359 
• 11 Brittain J. Gareau Y. Tetrahedron Lett.  1993,  34:  3363 
• 12a Abel EW. Walker DJ. J. Chem. Soc. A  1968,  2338 
• 12b Trost BM. Scanlan TS. Tetrahedron Lett.  1986,  27:  4141 
• 13a Steger BN. inventors; U. S. Patent  4564710.  ; Chem. Abstr. 1986, 105, 45235
• 13b Morishiri H, Shimakawa K, Ryu A, Kawato N, and Kobayashi S. inventors; Jpn. Kokai Tokkyo Koho JP  2003155269.  ; Chem. Abstr. 2004, 138, 385064
• 14 Bordwell FG. Anderson HM. J. Am. Chem. Soc.  1953,  75:  4959 
• 15 Justo de Pomar JC. Soderquist JA. Tetrahedron Lett.  1998,  39:  4409 
• 16 Degl’Innocenti A. Capperucci A. Castagnoli G. Malesci I. Synlett  2005,  1965 
• 18a Hanson RM. Chem. Rev.  1991,  91:  437 
• 18b Kim M.-J. Choi YK. J. Org. Chem.  1992,  57:  1605 
• 19 Dei S. Bellucci C. Buccioni M. Ferraroni M. Gualtieri F. Guandalini L. Manetti D. Matucci R. Romanelli MN. Scapecchi S. Teodori E. Bioorg. Med. Chem.  2003,  11:  3153 
• 20 Aversa MC. Barattucci A. Bonaccorsi P. Giannetto P. J. Org. Chem.  1997,  62:  4376 

17

Typical Procedure: A solution of 2-methyloxirane (1a, 100 mg, 1.72 mmol) and HMDST (470 µL, 2.24 mmol, 398 mg) in THF (0.1 mL) was treated at r.t. with TBAF (1 M in THF; 450 µL, 0.45 mmol) under an inert atmosphere. The mixture became bright green and after 5 min pale yellow. The reaction was carried out for 30 min and the progress of the reaction monitored by TLC. After addition of citric acid (50% aq solution; 0.5 mL) the mixture was stirred for 5 min, then diluted with Et₂O. The organic phase was then washed with citric acid (20% aq solution), extracted with Et₂O, and dried over Na₂SO₄. Evaporation of the solvent afforded 106 mg of 1-mercaptopropan-2-ol (2a; 65%), which was pure enough to be used without further purification. ¹H NMR (200 MHz, CDCl₃): δ = 1.25 (3 H, d, J = 6.0 Hz), 1.43 (1 H, app t, J = 8.7 Hz), 2.32 (1 H, br s), 2.44-2.56 (1 H, m), 2.60-2.71 (1 H, m), 3.71-3.84 (1 H, m). ¹³C NMR (50 MHz, CDCl₃): δ = 21.7, 33.2, 68.4. MS: m/z (%) = 92 (0.08), 91 (0.25), 75 (11), 45 (100).
Following the above procedure, oxirane 1a and HMDST were treated with a solution of TBAF (225 µL, 0.22 mmol)to give cleanly 2-(trimethylsilyloxy)propane-1-thiol (3a; 203 mg, 72% yield). ¹H NMR (200 MHz, CDCl₃): δ = 0.14 (9 H, s), 1.22 (3 H, d, J = 6.0 Hz), 1.46 (1 H, dd, J = 9.0 Hz, J = 8.8 Hz), 2.43-2.59 (2 H, m), 3.84 (1 H, app sextet). ¹³C NMR (50 MHz, CDCl₃): δ = 0.2, 22.5, 33.3, 70.0. MS: m/z (%) = 164 (0.6), 149 (10), 117 (66), 91 (15), 75 (53), 73 (100).