A new look at the McMurry reaction

Abstract

The article emphasizes the contradictory features of the McMurry reaction. The historical view shows how the chemists were firmly convinced of the occurrence of pinacolate intermediates and rejected, in spite of some evidence, the alternative pathway via carbenoid species. The McMurry reaction continues to find new important applications but suffers from problems of reproducibility. New practical reagents and simplified methods have been developed but rather complicated systems have been designed for obtaining higher selectivities. Recent investigations confirmed that pinacolates would be the precursors to alkenes but also revealed the possible involvement of carbenoid species, putting forward the dual nature of the mechanism of the McMurry reaction.

References

1. R. G. Dushin, in Comprehensive Organometallic Chemistry II, ed. L. S. Hegedus, Pergamon, Oxford, 1995, vol. 12, p. 1071; G. M. Robertson, in Comprehensive Organic Synthesis, ed. B. M. Trost, I. Fleming and G. Pattenden, Pergamon, Oxford, 1991, vol. 3, p. 563; Y. Dang and H. J. Geise, J. Organomet. Chem., 1991, 405, 1; J. E. McMurry, Chem. Rev., 1989, 89, 1513; C. Betschart and D. Seebach, Chimia, 1989, 43, 39; Y. Dang and H. J. Geise, Janssen Chim. Acta, 1989, 7, 3; 1988, 6, 3.
2. D. Lenoir, Synthesis, 1989, 883.
3. T. Letcka, in Active Metals. Preparation, Characterization, Applications, ed. A. Fürstner, VCH, Weinheim, 1996, p. 85.
4. A. Fürstner and B. Bogdanovic, Angew. Chem., Int. Ed. Engl., 1996, 35, 2442.
5. K. B. Sharpless, M. A. Umbreit, M. T. Nieh and T. C. Flood, J. Am. Chem. Soc., 1972, 94, 6538.
6. S. Tyrlik and I. Wolochowicz, Bull. Soc. Chim. Fr., 1973, 2147.
7. T. Mukaiyama, T. Sato and J. Hanna, Chem. Lett., 1973, 1041.
8. J. E. McMurry and M. P. Fleming, J. Am. Chem. Soc., 1974, 96, 4708.
9. Y. Fujiwara, R. Ishikawa, F. Akiyama and S. Teranishi, J. Org. Chem., 1978, 43, 2477.
10. J. C. Bryan and J. M. Mayer, J. Am. Chem. Soc., 1990, 112, 2298.
11. M. H. Chisholm, K. Folting and J. A. Klang, Organometallics, 1990, 9, 602.
12. M. H. Chisholm, K. Folting and J. A. Klang, Organometallics, 1990, 9, 607.
13. F. A. Cotton, D. DeMarco, L. R. Falvello and R. A. Walton, J. Am. Chem. Soc., 1982, 104, 7375.
14. I. Columbus and S. E. Biali, J. Org. Chem., 1994, 59, 3402.
15. A. Fürstner and A. Hupperts, J. Am. Chem. Soc., 1995, 117, 4468.
16. T. Itoh, H. Saitoh and S. Iwatsuki, J. Polym. Sci., Part A: Polym. Chem., 1995, 33, 1589.
17. D. L. J. Clive, K. S. K. Murthy, A. G. W. Wee, J. S. Prasad, G. V. J. da Silva, M. Majewski, P. C. Anderson, C. F. Evans, R. D. Haugen, L. D. Heerze and J. R. Barrie, J. Am. Chem. Soc., 1990, 112, 3018.
18. W. G. Dauben, T. Z. Wang and R. W. Stephens, Tetrahedron Lett., 1990, 2393.
19. J. E. McMurry and R. G. Dushin, J. Am. Chem. Soc., 1990, 112, 6942.
20. K. C. Nicolaou, J. J. Liu, Z. Yang, H. Ueno, E. J. Sorensen, C. F. Claiborne, R. K. Guy, C. K. Hwang, M. Nakada and P. G. Nantermet, J. Am. Chem. Soc., 1995, 117, 634; K. C. Nicolaou, Z. Yang, J. J. Liu, P. G. Nantermet, C. F. Claiborne, J. Renaud, R. K. Guy and K. Shibayama, J. Am. Chem. Soc., 1995, 117, 645.
21. A. Fürstner and G. Seidel, Synthesis, 1995, 63; A. Fürstner, G. Seidel, B. Gabor, C. Kopiske, C. Krüger and R. Mynott, Tetrahedron, 1995, 51, 8875.
22. A. Fürstner, A. Ernst, H. Krauze and A. Ptock, Tetrahedron, 1996, 52, 7329; A. Fürstner, A. Ptock, H. Weintritt, R. Goddard and C. Krüger, Angew. Chem., Int. Ed. Engl., 1995, 34, 678; A. Fürstner, H. Weintritt and A. Hupperts, J. Org. Chem., 1995, 60, 6637.
23. A. Fürstner, A. Hupperts, A. Ptock and E. Janssen, J. Org. Chem., 1994, 59, 5215.
24. J. E. McMurry and M. P. Fleming, J. Org. Chem., 1976, 41, 896; J. E. McMurry and L. R. Krepski, J. Org. Chem., 1976, 41, 3929.
25. J. E. McMurry, M. P. Fleming, K. L. Kees and L. R. Krepski, J. Org. Chem., 1978, 43, 3255.
26. J. E. McMurry, T. Letcka and J. G. Rico, J. Org. Chem., 1989, 54, 3748.
27. M. A. Barteau, Chem. Rev., 1996, 96, 1413; J. E. Rekoske and M. A. Barteau, Ind. Eng. Chem. Res., 1995, 34, 2931.
28. H. Idriss and M. A. Barteau, Langmuir, 1994, 10, 3693.
29. H. Idriss, K. G. Pierce and M. A. Barteau, J. Am. Chem. Soc., 1994, 116, 3063.
30. K. G. Pierce and M. A. Barteau, J. Org. Chem., 1995, 60, 2405.
31. B. Bogdanovic and A. Bolte, J. Organomet. Chem., 1995, 502, 109.
32. E. J. Corey, R. L. Danheiser and S. Chandrasekaran, J. Org. Chem., 1976, 41, 260.
33. A. Clerici and O. Porta, J. Org. Chem., 1985, 50, 76; A. Clerici, L. Clerici and O. Porta, Tetrahedron Lett., 1996, 37, 3035.
34. N. Balu, S. K. Nayak and A. Banerji, J. Am. Chem. Soc., 1996, 118, 5932.
35. O. Maury, C. Villiers and M. Ephritikhine, New J. Chem., 1997, 21, 137.
36. T. A. Lipski, M. A. Hilfiker and S. G. Nelson, J. Org. Chem., 1997, 62, 4566.
37. Y. Handa and J. Inanaga, Tetrahedron Lett., 1987, 28, 5717.
38. M. C. Barden and J. Schwartz, J. Am. Chem. Soc., 1996, 118, 5484.
39. A. Gansäuer, Synlett, 1997, 363.
40. R. Dams, M. Malinowski, I. Westdorp and H. Y. Geise, J. Org. Chem., 1982, 47, 248.
41. L. E. Aleandri, S. Becke, B. Bogdanovic, D. J. Jones and J. Rozière, J. Organomet. Chem., 1994, 472, 97.
42. J. J. Eisch, X. Shi and J. Lasota, Z. Naturforsch., Teil B, 1995, 50, 342.
43. M. Stahl, U. Pidun and G. Frenking, Angew. Chem., Int. Ed. Engl., 1997, 36, 2234.
44. R. S. P. Coutts, P. C. Wailes and R. L. Martin, J. Organomet. Chem., 1973, 50, 145; J. C. Huffman, K. G. Moloy, J. A. Marsella and K. G. Caulton, J. Am. Chem. Soc., 1980, 102, 3009; M. Pasquali, C. Floriani, A. Chiesi Villa and C. Guastini, Inorg. Chem., 1981, 20, 349.
45. O. Maury, M. Ephritikhine, M. Nierlich, M. Lance and E. Samuel, Inorg. Chim. Acta, in the press.
46. C. Villiers, R. Adam, M. Lance, M. Nierlich, J. Vigner and M. Ephritikhine, J. Chem. Soc., Chem. Comm., 1991, 1144.
47. O. Maury, C. Villiers and M. Ephritikhine, Angew. Chem., Int. Ed. Engl., 1996, 35, 1129.
48. M. Ephritikhine, O. Maury, C. Villiers, M. Lance and M. Nierlich, unpublished work.
49. C. Villiers and M. Ephritikhine, Angew. Chem., Int. Ed. Engl., 1997, 36, 2380.
50. M. A. Barteau, personal communication.