A novel tetrathiafulvalene building block

Synthesis

Volumn , Issue 5, 1999, Pages 803-810

  Jeppesen, Jan Oskar ^a   Takimiya, Kazuo ^a   Thorup, Niels ^b   Becher, Jan ^a  

^a UNIVERSITY OF SOUTHERN DENMARK   (Denmark)

^b TECHNICAL UNIVERSITY OF DENMARK   (Denmark)

Author keywords

Bromomethyl; Orthogonal sets of protection groups; Stepwise and asymmetrical bis functionalization; Tetrathiafulvalene building block; Thiocyanatomethyl

Indexed keywords

TETRATHIAFULVALENE DERIVATIVE;

ALKYLATION; ARTICLE; CRYSTAL STRUCTURE; REACTION ANALYSIS; SYNTHESIS;

EID: 0032912894     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-3473     Document Type: Article

References (35)

1. For reviews, see: Schukat, G.; Richter, A. M.; Fanghänel, E. Sulfur Reports 1987, 7, 155. Schukat, G.; Fanghänel, E. ibid 1993, 14, 245.
2. For reviews, see: Schukat, G.; Richter, A. M.; Fanghänel, E. Sulfur Reports 1987, 7, 155. Schukat, G.; Fanghänel, E. ibid 1993, 14, 245.
3. Bryce, M. R. Chem. Soc. Rev. 1991, 20, 355.
4. Jørgensen, T.; Hansen, T. K.; Becher, J. Chem. Soc. Rev. 1994, 23, 41.
5. Becher, J.; Li, Z.-T.; Blanchard, P.; Svenstrup, N.; Lau, J.; Nielsen, M. B.; Leriche, P. Pure & Appl. Chem. 1997, 69, 465.
6. Svenstrup; N.; Rasmussen, K. M.; Hansen, T. K.; Becher, J. Synthesis 1994, 809.
7. Simonsen, K. B.; Svenstrup, N.; Lau, J.; Simonsen, O.; Mørk, P.; Kristensen, G. J.; Becher, J. Synthesis 1995, 407.
8. Garin, J.; Orduna, J.; Uriel, J.; Moore, A. J.; Bryce, M. R; Wegener, S.; Yufit, D. S.; Howard, J. A. K. Synthesis 1994, 489.
9. Garin, J. Adv. Heterocycl. Chem. 1995, 62, 249.
10. Simonsen, K. B.; Becher, J. Synlett 1997, 1211.
11. For definition of orthogonal sets, see: Barany, G.; Merrifield, R. B. J. Am Chem. Soc. 1977, 99, 7363. Barany, G.; Albericio, F. J. ibid 1985, 107, 4936.
12. For definition of orthogonal sets, see: Barany, G.; Merrifield, R. B. J. Am Chem. Soc. 1977, 99, 7363. Barany, G.; Albericio, F. J. ibid 1985, 107, 4936.
13. Fox, A. F.; Pan, H. J. Org. Chem. 1994, 59, 6519.
14. 4,5-Bis(methoxycarbonyl)-1,3-dithiole-2-thione (1) is available in a one-step reaction between ethylene trithiocarbonate and dimethyl acetylendicarboxylate, see: Easton, D. B. J.; Leaver, D. J. Chem, Soc., Chem. Commun. 1965, 585. O'Connor, B. R.; Jones, F. N. J. Org. Chem. 1970, 35, 219.
15. 4,5-Bis(methoxycarbonyl)-1,3-dithiole-2-thione (1) is available in a one-step reaction between ethylene trithiocarbonate and dimethyl acetylendicarboxylate, see: Easton, D. B. J.; Leaver, D. J. Chem, Soc., Chem. Commun. 1965, 585. O'Connor, B. R.; Jones, F. N. J. Org. Chem. 1970, 35, 219.
16. Previous results have shown that an primary alcohol functionality is unable to survive the standard trialkyl phosphite coupling, whereas the tert-butyldiphenylsilyl alcohol protecting group is able to withstand the standard coupling conditions, see: Marshallsay, G. J; Bryce, M. R.; Cooke, G.; Jørgensen, T.; Becher, J.; Reynolds, C. D.; Wood, S. Tetrahedron 1993, 49, 6849. Marshallsay, G. J, Hansen, T. K.; Moore, A. J.; Bryce, M. R.; Becher, J. Synthesis 1995, 926. A tetrathiafulvalene bearing a secondary alcohol functionality has been produced by a trialkyl phosphite coupling in reasonable yield, see: Ozturk, T.; Rice, C.R.; Wallis, J.D. J. Mater Chem 1995, 5, 1553.
17. Previous results have shown that an primary alcohol functionality is unable to survive the standard trialkyl phosphite coupling, whereas the tert-butyldiphenylsilyl alcohol protecting group is able to withstand the standard coupling conditions, see: Marshallsay, G. J; Bryce, M. R.; Cooke, G.; Jørgensen, T.; Becher, J.; Reynolds, C. D.; Wood, S. Tetrahedron 1993, 49, 6849. Marshallsay, G. J, Hansen, T. K.; Moore, A. J.; Bryce, M. R.; Becher, J. Synthesis 1995, 926. A tetrathiafulvalene bearing a secondary alcohol functionality has been produced by a trialkyl phosphite coupling in reasonable yield, see: Ozturk, T.; Rice, C.R.; Wallis, J.D. J. Mater Chem 1995, 5, 1553.
18. Previous results have shown that an primary alcohol functionality is unable to survive the standard trialkyl phosphite coupling, whereas the tert-butyldiphenylsilyl alcohol protecting group is able to withstand the standard coupling conditions, see: Marshallsay, G. J; Bryce, M. R.; Cooke, G.; Jørgensen, T.; Becher, J.; Reynolds, C. D.; Wood, S. Tetrahedron 1993, 49, 6849. Marshallsay, G. J, Hansen, T. K.; Moore, A. J.; Bryce, M. R.; Becher, J. Synthesis 1995, 926. A tetrathiafulvalene bearing a secondary alcohol functionality has been produced by a trialkyl phosphite coupling in reasonable yield, see: Ozturk, T.; Rice, C.R.; Wallis, J.D. J. Mater Chem 1995, 5, 1553.
19. 60, see: Boulle, C.; Rabrcau, J. M.; Hudhomme, P.; Cariou, M.; Jubault, M.; Gorgues, A.; Orduna, J.; Garin, J. Tetrahedron Letters 1997, 38, 3909.
20. Richter, R.; Ulrich, H. The Chemistry of Cyanates and Their Thio Derivatives, Patai, S., Ed.; John Wiley & Sons: New York, 1977; Vol. 2, Chapter 17. Breitenbach, J.; Boosfeld, J.; Vögtle, F. Comprehensive Supramolecular Chemistry, Atwood, J. L.; Davies, J. E. D.; MacNicol, D. D., Vögtle, F.: Lehn, J.-L., Eds.; Pergamon: 1996, Vol. 2, Chapter 2.
21. Richter, R.; Ulrich, H. The Chemistry of Cyanates and Their Thio Derivatives, Patai, S., Ed.; John Wiley & Sons: New York, 1977; Vol. 2, Chapter 17. Breitenbach, J.; Boosfeld, J.; Vögtle, F. Comprehensive Supramolecular Chemistry, Atwood, J. L.; Davies, J. E. D.; MacNicol, D. D., Vögtle, F.: Lehn, J.-L., Eds.; Pergamon: 1996, Vol. 2, Chapter 2.
22. 2O to a mixture of 7 and MeI.
23. Hudhomme, P.; Blanchard, P.; Sallé, M,; Moustarder, S. L.; Riou, A.; Jubault, M.; Gorgues, A.; Duguay, G. Angew. Chem. Int. Ed. Engl. 1997, 36, 878.
24. Durand, C.; Hudhomme, P.; Duguay, G.; Jubault, M.; Gorgues, A. J. Chem. Soc., Chem. Commun. 1998, 361.
25. Attempt to deprotect the remaining two cyanoethyl thiolate protecting groups in 8d followed by addition of iodomcthane failed, probably due to the unstability of the disulfide moiety.
26. 4 to 7 in THF/EtOH (2:1) followed by addition of deoxygenated water and pH adjustment (pH = 7).
27. 4 should be used.
28. The orange solid exclusively contains tetrakis(2-cyanoethylthio)tetrathiafulvalene (TLC and PDMS).
29. f0.4, eluent EtOAc) was eluted with EtOAc until the solution was colourless (ca 2 L). This fraction contains trace of the above colourless impurity. Evaporation of the solvent in vacuo (T < 30 °C) gave a orange solid. Recrystallization from propan-2-ol (85 mL) gave the product 5 as thin orange needles with a slight decrease in the yield (81%).
30. 6) disappeared very fast.
31. The calculated values are based on the exact mass for compound 6 and for the molecular mass for compound 7.
32. Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.
33. Sheldrick, G. M. SHELXL97. Program for the Refinement of Crystal Structures, 1997, University of Göttingen, Germany.
34. Spek, A .L. Acta Crystallogr. 1990, A46, C-34.
35. Sheldrick, G. M. SHELXTL. Structure Determination Programs, Version 5.10., 1997, Broker (formerly Siemens) Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA.