Facile [2,3]-rearrangements of difluoroallylic alcohols with C-P and C-S bond formation

Tetrahedron Letters

Volumn 37, Issue 35, 1996, Pages 6403-6406

  Blades, Kevin ^a   Patel, Sunita T ^a   Percy, Jonathan M ^a   Wilkes, Robin D ^a  

^a UNIVERSITY OF BIRMINGHAM   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; ORGANOFLUORINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030603085     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01358-5     Document Type: Article

References (20)

1. 1. Evans, D.A.; Andrews, G.C. Acc. Chem. Res., 1974, 7, 147; Bravermann, S. in The Chemistry of Sulfones and Sulfoxides, ed. by Patai, S.; Rappoport, Z.; Stirling, C.J.M. John Wiley, London, 1988, Chapter 14.
2. 1. Evans, D.A.; Andrews, G.C. Acc. Chem. Res., 1974, 7, 147; Bravermann, S. in The Chemistry of Sulfones and Sulfoxides, ed. by Patai, S.; Rappoport, Z.; Stirling, C.J.M. John Wiley, London, 1988, Chapter 14.
3. 2. Boisselle, A.P.; Meinhardt, N.A. J. Org. Chem., 1962, 27, 1828.
4. 3. Janecki, T.; Bodalski, R. Synthesis, 1990, 799.
5. 4. Berkowitz, D.B.; Sloss, D.G. J. Org. Chem., 1995, 60, 7047 and references therein.
6. 5. Sabol, J.S.; McCarthy, J.R. Tetrahedron Lett., 1992, 33, 3101; Stahly, G.P. J. Fluorine Chem., 1989, 43, 53: recently, α-chloro-α-fluorosulfoxides were described; see Jouen, C.; Lasne, M.C.; Pommelet, J.C. Tetrahedron Lett., 1996, 37, 2413.
7. 5. Sabol, J.S.; McCarthy, J.R. Tetrahedron Lett., 1992, 33, 3101; Stahly, G.P. J. Fluorine Chem., 1989, 43, 53: recently, α-chloro-α-fluorosulfoxides were described; see Jouen, C.; Lasne, M.C.; Pommelet, J.C. Tetrahedron Lett., 1996, 37, 2413.
8. 5. Sabol, J.S.; McCarthy, J.R. Tetrahedron Lett., 1992, 33, 3101; Stahly, G.P. J. Fluorine Chem., 1989, 43, 53: recently, α-chloro-α-fluorosulfoxides were described; see Jouen, C.; Lasne, M.C.; Pommelet, J.C. Tetrahedron Lett., 1996, 37, 2413.
9. 6. Patel, S.T.; Percy, J.M.; Wilkes, R.D. Tetrahedron, 1995, 51, 11327.
10. 7. Brominative and chlorinative transpositions of this type were described recently; see Tellier, F.; Sauvêtre, R. J. Fluorine Chem., 1996, 76, 79.
11. 8. Patel, S.T.; Percy, J.M.; Wilkes, R.D. J. Org. Chem., 1996, 61, 166.
12. 9. Patel, S.T.; Percy, J.M.; Wilkes, R.D. Tetrahedron, 1995, 51, 9201.
13. 10. In a typical procedure, phenylsulfenyl chloride (1.5 eq.) was added slowly to a solution of the difluoroallylic alcohol (0.1 M in dichloromethane) containing triethylamine (1.2 eq.) at -78 °C. After 1 hour at that temperature, the mixture was allowed to warm to -30 °C (sulfur electrophiles) or room temperature (phosphorus electrophiles) overnight. Sulfoxide and phosphine oxide products were purifed by flash column chromatography after aqueous work-up.
14. +) 340.10303, found 340.10342.
15. 12. Tang, R.; Mislow, K. J. Am. Chem. Soc., 1970, 92, 2100.
16. 13. Dolbier, W.R.; Medinger, K.S.; Greenberg, A.; Liebman, J.F. Tetrahedron, 1982, 38, 2415.
17. 14. When the reaction of primary allylic alcohol 1b with chloro diphenylphosphine was run in dry undegassed dichloromethane, oxidised product 8 was isolated in 21% yield. In dichloromethane that had been purged with dry argon, only 6b was obtained (68%).
18. 15. Initial attempts to phosphitylate with commercial diethyl chlorophosphite failed to afford phosphonate products with or without added DMAP. We are exploring currently other phosphitylating agents.
19. 16. Sulfone-containing peptidomimetics have been described recently: Rivero, R.A.;. Greenlee, W.J.; Patchett, A.A. Tetrahedron Lett., 1991, 32, 5263; Jungheim, L.N.; Shepherd, T.A.; Baxter, A.J.; Burgess, J.; Hatch, S.D.; Lubbehusen, P.; Wiskerchen, M.; Muesing, M.A. J. Med. Chem., 1996, 39, 96.
20. 16. Sulfone-containing peptidomimetics have been described recently: Rivero, R.A.;. Greenlee, W.J.; Patchett, A.A. Tetrahedron Lett., 1991, 32, 5263; Jungheim, L.N.; Shepherd, T.A.; Baxter, A.J.; Burgess, J.; Hatch, S.D.; Lubbehusen, P.; Wiskerchen, M.; Muesing, M.A. J. Med. Chem., 1996, 39, 96.