Synthesis of Fluoroalkyl Vinyl Sulfoxides and their Use in Diels-Alder Reactions

Abstract

Condensation of various dienes with fluoroalkyl vinyl sulfoxides was studied. Four diastereoisomers were obtained in the case of cyclopentadiene and their structures were assigned by 2D NMR experiments. Diels-Alder cycloaddition occurred with cyclohexadiene, in comparison to phenyl vinyl sulfoxide, without thermal extrusion of fluoroalkylsulfenic acid. Condensation with anthracene led to a mixture of compounds 11 and 12.

Key words

acetylene equivalent - Diels-Alder reactions - eliminations - fluorine - sulfoxides

References

• 1 Redon M. Janousek Z. Viehe HG. Tetrahedron  1997,  53:  6861 
• 2 Sridhar M. Krishna KL. Rao JM. Tetrahedron  2000,  56:  3539 
• 3 Krasovsky AL. Pissarev SA. Nenajdenko VA. Balenkova ES. J. Chem. Soc., Perkin Trans. 1  2002,  2554 
• 4 Ronan B. Kagan H. Tetrahedron: Asymmetry  1991,  2:  75 
• 5 Fernandez A. Khiar N. Chem. Rev.  2003,  103:  3651 
• 6 Paquette LA. Moerck RE. Harichian B. Magnus PD. J. Am. Chem. Soc.  1978,  100:  1597 
• 7 Eguchi S. Ishiura K. Noda T. Sasaki T. J. Org. Chem.  1987,  52:  496 
• 8 Koreeda M. Jung K. Ichita J. J. Chem. Soc., Perkin Trans. 1  1989,  2129 
• 9 Williams RV. Lin X. J. Chem. Soc., Chem. Commun.  1989,  1872 
• 10 Lautens M. Edwards LG. Tetrahedron Lett.  1989,  30:  6813 
• 11 De Lucchi O. Modena G. Tetrahedron  1984,  40:  2585 
• 12 Hansch C. Leo A. Taft RW. Chem. Rev.  1991,  91:  165 
• 13 Magnier E. Tordeux M. Goumont R. Magder K. Wakselman C. J. Fluorine Chem.  2003,  114:  55 
• 14 Matsnev AV. Kondratenko NV. Yagupolskii YL. Yagupolskii LM. Tetrahedron Lett.  2002,  43:  2949 
• 16 Danishefsky S. Harayama T. Singh RK. J. Am. Chem. Soc.  1979,  101:  7008 
• 17 Ji X. Van der Helm D. Williams RV. Ebey WJ. Acta Crystallogr. Sect. B  1989,  45:  93 
• 18 Garcia Ruano JL. Martin Castro AM. Rodriguez Ramos JH. Heteroat. Chem.  2002,  13:  453 
• 19 Fringuelli F. Tatiechi A. In Dienes in the Diels-Alder Reaction   Wiley; New York: 1990.  p.179 
• 20 Maignan C. Raphael RA. Tetrahedron  1983,  39:  3245 
• 21 Trost BM. Chem. Rev.  1978,  78:  363 
• 22 Mc Culla RD. Jenks WS. J. Am. Chem. Soc.  2003,  125:  7871 
• 23 Ono N. Miyake H. Kamimura A. Tsukui N. Kaji A. Tetrahedron Lett.  1982,  23:  2957 

15

The literature indicates that the cycloaddition of Danishefsky’s diene with phenyl vinyl sulfoxide required temperatures of ca. 135-150 °C without description of the products formed.