Solvent-free organic syntheses . using supported reagents and microwave irradiation

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Rajender S. Varma


Recent developments in microwave-accelerated solventless organic syntheses are summarised. This expeditious and solvent-free approach involves the exposure of neat reactants to microwave (MW) irradiation in conjunction with the use of supported reagents or catalysts which are primarily of mineral origin. The salient features of these high yield protocols are the enhanced reaction rates, greater selectivity and the experimental ease of manipulation. Among other reagents recently described in the literature on this eco-friendly green approach, the use of recyclable mineral oxides or supported reagents from our laboratory such as Fe(NO3)3–clay (clayfen), Cu(NO3)2–clay (claycop), NH4NO3–clay (clayan), NH2OH–clay, PhI(OAc)2–alumina, NaIO4–silica, CrO3–alumina, MnO2–silica, NaBH4–clay, etc. are highlighted in MW-promoted deprotection, condensation, cyclization, rearrangement, oxidation and reduction reactions including the rapid one-pot assembly of heterocyclic compounds from in situ generated intermediates.


References

  1. Using chemical reagents on porous carriers, Akt.-Ges. Fur Chemiewerte, Br. Pat., 1924, 231, 901 Search PubMed ; Chem. Abstr., 1925, 19, 3571 Search PubMed .
  2. (a) G. H. Posner, Angew. Chem., Int. Ed. Engl., 1978, 17, 487 CrossRef ; (b) A. McKillop and K. W. Young, Synthesis, 1979, 401 and 481 CrossRef CAS .
  3. (a) A. Cornelis and P. Laszlo, Synthesis, 1985, 909 CrossRef CAS ; (b) P. Laszlo, Preparative Chemistry Using Supported Reagents, Academic Press, Inc., San Diego, 1987 Search PubMed ; (c) K. Smith, Solid Supports and Catalyst in Organic Synthesis, Ellis Horwood, Chichester, 1992 Search PubMed ; (d) M. Balogh and P. Laszlo, Organic Chemistry Using Clays, Springer-Verlag, Berlin, 1993 Search PubMed ; (e) J. H. Clark, Catalysis of Organic Reactions by Supported Inorganic Reagents, VCH Publishers, Inc., NY, 1994 Search PubMed ; (f) J. H. Clark and D. J. Macquarrie, Chem. Commun., 1998, 853 RSC ; (g) G. W. Kabalka and R. M. Pagni, Tetrahedron, 1997, 53, 7999 CrossRef CAS .
  4. R. Gedye, F. Smith, K. Westaway, H. Ali, L. Baldisera, L. Laberge and J. Rousell, Tetrahedron Lett., 1986, 27, 279 CrossRef CAS .
  5. For recent reviews on microwave-assisted chemical reactions see: (a) R. A. Abramovich, Org. Prep. Proc. Int., 1991, 23, 683 CAS ; (b) A. G. Whittaker and D. M. P. Mingos, J. Microwave Power Electromagnetic Energy, 1994, 29, 195 Search PubMed ; (c) S. Caddick, Tetrahedron, 1995, 51, 10403 CrossRef ; (d) C. R. Strauss and R. W. Trainor, Aust. J. Chem., 1995, 48, 1665 CrossRef CAS ; (e) A. K. Bose, B. K. Banik, N. Lavlinskaia, M. Jayaraman and M. S. Manhas, CHEMTECH, 1997, 27, 18 CAS ; (f) R. S. Varma, Clean Products and Processes, 1999, in press Search PubMed .
  6. R. J. Giguere, A. M. Namen, B. O. Lopez, A. Arepally, D. E. Ramos, G. Majetich and J. Defrauw, Tetrahedron Lett., 1987, 28, 6553 CrossRef CAS .
  7. R. S. Varma, in, Microwaves: Theory and Application in Material Processing IV, ed. D. E. Clark, W. H. Sutton and D. A. Lewis, American Ceramic Society, Westerville, OH, 1997, pp. 357–365 Search PubMed .
  8. R. S. Varma and H. M. Meshram, Tetrahedron Lett., 1997, 38, 5427 CrossRef CAS .
  9. R. S. Varma and R. K. Saini, Tetrahedron Lett., 1997, 38, 2623 CrossRef CAS .
  10. R. S. Varma, M. Varma and A. K. Chatterjee, J. Chem. Soc., Perkin Trans. 1, 1993, 999 RSC .
  11. R. S. Varma, A. K. Chatterjee and M. Varma, Tetrahedron Lett., 1993, 34, 3207 CrossRef CAS .
  12. R. S. Varma, J. B. Lamture and M. Varma, Tetrahedron Lett., 1993, 34, 3029 CrossRef CAS .
  13. R. S. Varma, A. K. Chatterjee and M. Varma, Tetrahedron Lett., 1993, 34, 4603 CrossRef CAS .
  14. R. S. Varma, R. Dahiya and R. K. Saini, Tetrahedron Lett., 1997, 38, 8819 CrossRef CAS .
  15. R. S. Varma and H. M. Meshram, Tetrahedron Lett., 1997, 38, 7973 CrossRef CAS .
  16. R. S. Varma and D. Kumar, Synth. Commun., 1999, 29 Search PubMed  in press.
  17. R. S. Varma and R. Dahiya, Tetrahedron Lett., 1997, 38, 2043 CrossRef CAS .
  18. R. S. Varma, R. K. Saini and R. Dahiya, Tetrahedron Lett., 1997, 38, 7823 CrossRef CAS .
  19. R. S. Varma and R. Dahiya, Tetrahedron Lett., 1998, 39, 1307 CrossRef CAS .
  20. R. S. Varma and R. K. Saini, Tetrahedron Lett., 1998, 39, 1481 CrossRef CAS .
  21. R. S. Varma, R. Dahiya and R. K. Saini, Tetrahedron Lett., 1997, 38, 7029 CrossRef CAS .
  22. R. S. Varma, D. Kumar and R. Dahiya, J. Chem. Res. (S), 1998, 324 RSC .
  23. R. S. Varma, R. Dahiya and D. Kumar, Molecules Online, 1998, 2, 82 CrossRef CAS .
  24. R. S. Varma, R. K. Saini and H. M. Meshram, Tetrahedron Lett., 1997, 38, 6525 CrossRef CAS .
  25. (a) R. S. Varma, R. K. Saini and R. Dahiya, J. Chem. Res. (S), 1998, 120 RSC ; (b) R. S. Varma and R. Dahiya, Synth. Commun., 1998, 28, 4087 CrossRef CAS .
  26. R. S. Varma, R. Dahiya and S. Kumar, Tetrahedron Lett., 1997, 38, 2039 CrossRef CAS .
  27. R. S. Varma and R. Dahiya, Synlett, 1997, 1245 CAS .
  28. R. S. Varma, R. Dahiya and S. Kumar, Tetrahedron Lett., 1997, 38, 5131 CrossRef CAS .
  29. R. S. Varma and R. Dahiya, J. Org. Chem., 1998, 63, 8038 CrossRef CAS .
  30. R. S. Varma, R. K. Saini and D. Kumar, J. Chem. Res. (S), 1998, 348 RSC .
  31. R. S. Varma and R. K. Saini, Synlett, 1997, 857 CAS .
  32. R. S. Varma and R. K. Saini, Tetrahedron Lett., 1997, 38, 4337 CrossRef CAS .
  33. R. S. Varma and R. Dahiya, Tetrahedron, 1998, 54, 6293 CrossRef CAS .
  34. (a) D. Villemin and B. Labiad, Synth. Commun., 1990, 20, 3333 CAS ; (b) D. Villemin and A. B. Alloum, Synth. Commun., 1990, 20, 3325 CAS ; (c) D. Villemin and A. B. Alloum, Synth. Commun., 1991, 21, 63 ; (d) J. M. Lerestif, J. P. Bazureau and J. Hamelin, Synlett, 1995, 647 CrossRef CAS ; (e) M. Csiba, J. Cleophax, A. Loupy, J. Malthete and S. D. Gero, Tetrahedran Lett., 1993, 34, 1787 CrossRef CAS ; (f) D. Villemin, A. B. Alloum and F. Thibault-Starzyk, Synth. Commun., 1992, 22, 1359 CAS ; (g) H. Benhaliliba, A. Derdour, J.-P. Bazureau, F. Texier-Boullet and J. Hamelin, Tetrahedron Lett., 1998, 39, 541 CrossRef CAS ; (h) M. Rahmouni, A. Derdour, J.-P. Bazureau and J. Hamelin, Tetrahedron Lett., 1994, 35, 4563 (, ) CrossRef CAS ; Synth. Commun., 1996, 26, 453 Search PubMed ; (i) E. Gutierrez, A. Loupy, G. Bram and E. Ruiz-Hitzky, Tetrahedron Lett., 1989, 30, 945 CrossRef CAS ; (j) D. Villemin and B. Labiad, Synth. Commun., 1992, 22, 2043 CAS ; (k) A. I. Bosch, P. de la Cruez, E. Diez-Barra, A. Loupy and F. Langa, Synlett, 1995, 1259 CrossRef CAS ; (l) D. Villemin and B. Martin, J. Chem. Res. (S), 1994, 146 Search PubMed .
  35. D. A. Nelson, C. Devin, S. Hoffmann and A. Lau, Division of Chemical Education, ACS National Meeting, San Francisco, April 13–17, 1997, Abstract no. 101 .
  36. M. Balogh and P. Laszlo, Organic chemistry using clays, Springer, Berlin, 1993 Search PubMed .
  37. B. Perio, M. J. Dozias, P. Jacquault and J. Hamelin, Tetrahedron Lett., 1997, 38, 7867 CrossRef CAS .
  38. D. Bogdal, J. Pielichowski and A. Boron, Synlett, 1996, 873 CrossRef CAS .
  39. A. Vass, J. Toth and E. Pallai-Varsanyi, Effect of inorganic solid support for microwave assisted organic reactions, OR 19, presented at the International Conference on Microwave Chemistry, Prague, Czech Republic, Sept. 6–11, 1998 Search PubMed .
  40. D. Bogdal, J. Pielichowski and K. Jaskot, Synth. Commun., 1997, 27, 1553 CAS .
  41. D. Bogdal, J. Pielichowski and K. Jaskot, Heterocycles, 1997, 45, 715 CAS .
  42. P. de la Cruz, A. de la Hoz, L. M. Font, F. Langa and M. C. Perez-Rodriguez, Tetrahedron Lett., 1998, 39, 6053 CrossRef CAS .
  43. (a) R. Ballini, M. Bordoni, G. Bosica, R. Maggi and G. Sartori, Tetrahedron Lett., 1998, 39, 7587 CrossRef CAS ; (b) R. Ballini, G. Bosica and M. Parrini, Tetrahedron Lett., 1998, 39, 7963 CrossRef CAS .
  44. D. Subhas Bose and V. Lakshminarayana, Tetrahedron Lett., 1998, 39, 5631 CrossRef CAS .
  45. (a) Comprehensive Organic Synthesis (Oxidation), ed. B. M. Trost, Pergamon, New York, 1991, vol 7 Search PubMed ; (b) A. Oussaid and A. Loupy, J. Chem. Res. (S), 1997, 342 RSC .
  46. (a) R. S. Varma and G. W. Kabalka, Heterocycles, 1986, 24, 2645 CrossRef CAS ; (b) G. W. Kabalka and R. S. Varma, Org. Prep. Proc. Int., 1987, 19, 283 CrossRef CAS ; (c) G. W. Kabalka, L. H. M. Guindi and R. S. Varma, Tetrahedron, 1990, 46, 7443 CrossRef CAS .
  47. D. Villemin and B. Martin, Synth. Commun., 1995, 25, 3135 .
  48. (a) V. Singh, J. Singh, P. Kaur and G. L. Kad, J. Chem. Res. (S), 1997, 58 RSC ; (b) D. Bogdal, J. Chem. Res. (S), 1998, 468 RSC .
  49. (a) G. H. Posner, A. W. Runquist and M. J. Chapdelaine, J. Org. Chem., 1977, 42, 1202 CrossRef CAS  and references cited therein; (b) D. Barbry and S. Torchy, Tetrahedron Lett., 1997, 38, 2959 CrossRef CAS .
  50. A. Saoudi, J. Hamelin and H. Benhaoua, J. Chem. Res. (S), 1996, 492 Search PubMed .
  51. D. Villemin, M. Hammadi and B. Martin, Synth. Commun., 1996, 26, 2895 CAS .
  52. A. L. Marrero-Terrero and A. Loupy, Synlett, 1996, 245 CrossRef CAS .
  53. R. S. Varma, D. Kumar and P. J. Liesen, J. Chem. Soc., Perkin Trans. 1, 1998, 4093 RSC .
  54. M. Miller and G. Loudon, J. Org. Chem., 1975, 40, 126 CrossRef CAS .
  55. (a) J. H. Pomeroy and C. A. Craig, J. Am. Chem. Soc., 1959, 81, 6340 CrossRef CAS ; (b) D. T. Mowry, Chem. Rev., 1948, 42, 250 ; (c) H. M. Sampath Kumar, P. K. Mohanty, M. Suresh Kumar and J. S. Yadav, Synth. Commun., 1997, 27, 1327 CAS ; (d) D. L. Clive, Chem. Commun., 1970, 1014 RSC ; (e) P. J. Foley, J. Org. Chem., 1969, 34, 2805 CrossRef CAS ; (f) W. Lehnert, Tetrahedron Lett., 1971, 6, 559 CrossRef ; (g) G. Rosini, G. Baccolini and S. Cacchi, J. Org. Chem., 1973, 38, 1060 CrossRef CAS ; (h) H. G. Foley and D. R. Dalton, J. Chem. Soc., Chem. Commun., 1973, 628 RSC ; (i) D. Villemin, M. Lalaoui and A. B. Alloum, Chem. Ind. (London), 1991, 176 CAS ; (j) R. S. Varma and K. P. Naicker, Molecules Online, 1998, 2, 94 CrossRef CAS ; (k) R. S. Varma, K. P. Naicker, D. Kumar, R. Dahiya and P. J. Liesen, J. Microwave Power Electromagnetic Energy, 1999, in press Search PubMed .
  56. (a) S. Cannizzaro, Ann., 1853, 88, 129 Search PubMed ; (b) T. A. Geissman, Org. React., (NY), 1944, II, 94 .
  57. (a) C. G. Swain, A. L. Powell, W. A. Sheppard and C. R. Morgan, J. Am. Chem. Soc., 1979, 101, 3576 CrossRef CAS ; (b) S. K. Chung, J. Chem. Soc., Chem. Commun., 1982, 480 RSC ; (c) E. C. Ashby, D. T. Coleman III and M. P. Gamasa, Tetrahedron Lett., 1983, 24, 851 CrossRef CAS .
  58. (a) R. S. Varma, K. P. Naicker and P. J. Liesen, Tetrahedron Lett., 1998, 39, 8437 CrossRef CAS ; (b) R. S. Varma, G. W. Kabalka, L. T. Evans and R. M. Pagni, Synth. Commun., 1985, 15, 279 CrossRef CAS .
  59. (a) J. Barrios, R. Rojas, A. R. Alcanrara and J. V. Sinisterra, J. Catal., 1988, 112, 528 CAS ; (b) J. V. Sinisterra, J. M. Marinas, F. Riquelme and M. S. Arias, Tetrahedron, 1988, 44, 1431 CrossRef CAS .
  60. J. V. Sinisterra, A. Fuentes and J. M. Marinas, J. Org. Chem., 1987, 52, 3875 CrossRef CAS .
  61. J. V. Sinisterra and J. M. Marinas, Bull. Soc. Chim. Belg., 1987, 96, 293 CAS .
  62. J. V. Sinisterra, React. Kinet. Catal. Lett., 1986, 30, 93 CAS .
  63. R. S. Varma, K. P. Naicker and P. J. Liesen, Tetrahedron Lett., 1998, 39, 3977 CrossRef CAS .
  64. D. Villemin and F. Sauvaget, Synlett, 1994, 435 CrossRef .
  65. A. Loupy and LeNgoc Thach, Synth. Commun., 1993, 23, 2571 CAS .
  66. (a) K. E. Wilzbach, J. Am. Chem. Soc., 1957, 79, 1013 CrossRef CAS ; (b) J. R. Jones, Development of new microwave enhanced tritiation procedures, OR 9, presented at the International Conference on Microwave Chemistry, Prague, Czech Republic, Sept. 6–11, 1998 Search PubMed ; (c) N. H. Werstiuk, in Isotopes in the physical and biological sciences, ed. E. Buncel and J. R. Jones, Elsevier, Amsterdam, 1987, vol. 1A, pp. 124–155 Search PubMed ; (d) S. Anto, J. R. Jones and S. Y. Lu, Microwave enhanced acidcatalysed hydrogen/deuterium exchange reactions, P 34, presented at the International Conference on Microwave Chemistry, Prague, Czech Republic, Sept. 6–11, 1998 Search PubMed .
  67. S. Stone-Elander, N. Elander, J.-O. Thorell, P. Johnstrom, H. Ehrsson, A. Andersson and S. Kalhori, Monomodal microwave techniques in microscale organic chemistry, OR 2, presented at the International Conference on Microwave Chemistry, Prague, Czech Republic, Sept. 6–11, 1998 and references cited therein Search PubMed .
  68. M. Liagre, A. Loupy, A. Oussaid, A. Petit and J. Cleophax, Scalingup of some typical organic reactions under focused microwaves, presented at the International Conference on Microwave Chemistry, Prague, Czech Republic, Sept. 6–11, 1998 Search PubMed .
  69. M. Mehdizadeh, Engineering and scale-up considerations for microwave induced reactions, in Proceedings: Microwave-Induced Reactions Workshop, Electric Power Research Institute, Palo Alto, CA, 1993, p. A-7 Search PubMed .