A convenient synthesis of dimethyl (diazomethyl)phosphonate (Seyferth/Gilbert reagent)

Journal of Organic Chemistry

Volumn 61, Issue 7, 1996, Pages 2540-2541

  Brown, Dean G ^a   Velthuisen, Emil J ^b   Commerford, Jessica R ^b   Brisbois, Ronald G ^b   Hoye, Thomas R ^a  

^a UNIVERSITY OF MINNESOTA   (United States)

^b HAMLINE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001517035     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951944n     Document Type: Article

References (22)

1. Presidential Faculty Fellow 1993-1995.
2. (a) Seyferth, D.; Marmor, R. S.; Hilbert, P J. Org. Chem 1971, 36, 1379.
3. (b) For an alternative preparation see: Ratcliffe, R.; Christensen, B. Tetrahedron Lett. 1973, 4645.
4. (c) Gilbert, J. C.; Weerasooriya, U. J. Org. Chem. 1982, 47, 1837.
5. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
6. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
7. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
8. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
9. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
10. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
11. For applications in natural product total synthesis see: (a) Nerenberg, J. B.; Hung, D. T.; Somers, P. K.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 12621. (b) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (c) Heathcock, C. H.; Clasby, M.; Griffith, D. A.; Henke, B. R.; Sharp, M. J. Synlett. 1995, 467. (d) Delpech, B.; Lett, R. Tetrahedron Lett. 1989, 30, 1521. For other applications see: (e) Gilbert, J. C.; Giamalva, D. H.; Weerasooriya, U. J. J. Org. Chem. 1983, 48, 5251. (f) Gilbert, J. C.; Giamalva, D. H.; Baze, M. E. J. Org. Chem. 1985, 50, 2557. (g) Walborsky, H. M. Topolski, M. J. Org. Chem. 1994, 59, 5506.
12. (a) Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 3769.
13. (b) Motherwell, W. B.; Lewis, R. T. Tetrahedron 1992, 48, 1465.
14. (c) Ohira, S.; Okai, K.; Moritani, T. J. Chem. Soc., Chem Commun. 1992, 721.
15. (d) Taber, D. F.; Walter, R.; Meagley, R. P. J. Org. Chem. 1994, 59, 6014.
16. Ohira, S. Synth. Commun. 1989, 19, 561.
17. Danheiser, R. L.; Miller, R. F.; Brisbois, R. G.; Park, S. Z. J. Org. Chem. 1990, 55, 1960.
18. Although we have fully characterized 6 as shown, the (dehydrated) keto form is almost certainly the reactive species in the diazo transfer and deacylation steps. We have not studied this equilibrium in detail.
19. Davies, H. M. L.; Smith, H. D.; Baum, J. S.; Shook, D. A. Synth. Commun. 1987, 17, 1709. In our preparations of p-ABSA we have used a slightly modified procedure (see Experimental Section).
20. For examples of methanesulfonyl azide in diazo transfer reactions, see: Taber, D. F.; Ruckle, R. E.; Hennessy, M. J. J. Org. Chem. 1986, 51, 4077.
21. Reproducibility of yields in the diazo transfer step varied to a greater degree using commercially available p-ABSA (20-50%) as compared to reactions in which the azide had been prepared in house (45-50%).
22. In optimizing this procedure we found that minimal exposure to aqueous solutions at this stage resulted in greater yields in the diazo transfer step.