Addition of Thiols to Sulfonylacetylenes: Synthetic Applications

Abstract

The addition of propane-1,3-dithiol to p-toluenesulfo­nylacetylene affords the dithioacetal 1. This compound is a useful building block for the synthesis of new functionalized sulfanylvinylsulfonyl derivatives.

Key words

dithioacetals - base-induced - ring-opening - S-alkylation - sulfanylvinylsulfonyl derivatives

References

• 1a Stirling CJM. J. Chem. Soc.  1964,  5856 
• 1b For a review on the chemistry of acetylenic and allenic sulfones, see: Back TG. Tetrahedron  2001,  57:  5263 ; the addition of thiols, sulfinates and related nucleophiles is considered in pp 5276-5277
• 2 Selling HA. Tetrahedron  1975,  31:  2387 
• 3 Tichenor GJW. Truce WE. J. Org. Chem.  1972,  37:  2391 
• 4a Arjona O. Iradier F. Medel R. Plumet J. J. Org. Chem.  1999,  64:  6090 
• 4b Arjona O. Medel R. Rojas JK. Costa AM. Vilarrasa J. Tetrahedron Lett.  2003,  44:  6369 
• 5 Medel R. Monterde MI. Plumet J. Rojas JK. J. Org. Chem.  2005,  70:  735 
• For the synthesis of oxathianes and dithianes by stereoselective addition-cyclization of hydroxythiols and dithiols to electron-poor acetylenes, see:
• 6a De Lucci O. Marchioro C. Modena G. Lucchini V. Tetrahedron Lett.  1985,  26:  4539 
• 6b De Lucci O. Marchioro C. Modena G. Lucchini V. Valle G. J. Org. Chem.  1986,  51:  1457 
• For the synthesis of acyclic and the cyclic thioacetal 5 (Figure 2) by base-catalyzed addition of ethanedithiol to arylsulfonylacetylenes, see:
• 6c Buso M. De Lucci O. Modena G. Tetrahedron Lett.  1987,  28:  107 
• 6d Cossu S. De Lucci O. Fabris F. Ballini R. Bosica G. Synthesis  1996,  1481 
• 8 Kruse CG. Janse ACV. Dert V. Van der Gen A. J. Org. Chem.  1979,  44:  2916 
• 9 Marshal JA. Sertz DE. J. Org. Chem.  1975,  40:  534 
• 10a Hase TA. Latineen L. Tetrahedron Lett.  1981,  22:  3285 
• 10b Hase TA. Latineen L. J. Organomet. Chem.  1982,  240:  9 
• 11 Mroskowski C. Manna S. Falck JR. Tetrahedron Lett.  1984,  25:  519 
• 12 Simpkins NS. Sulphones in Organic Synthesis   Pergamon; London: 1993. 

7

The reaction of propane-1,3-dithiol and p-toluenesulfonylacetylene in presence of Me₃P (THF) affords a mixture of compounds 6 and 7 (mixture of diastereomers) (Figure [3] ).

Figure 3 Compounds 6 and 7