Selective site controlled nucleophilic attacks in 5-membered ring phosphate esters: Unusual C-O vs. common P-O bond cleavage

Chemical Communications

Volumn , Issue 47, 2005, Pages 5879-5881

  Ashkenazi, Nissan ^a   Zade, Sanjio S ^b   Segall, Yoffi ^a   Karton, Yishai ^a   Bendikov, Michael ^b  

^a ISRAEL INSTITUTE FOR BIOLOGICAL RESEARCH   (Israel)

^b WEIZMANN INSTITUTE OF SCIENCE   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

ESTER; PHOSPHATE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; HYDROLYSIS; METHYLATION;

EID: 29644441883     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b512117e     Document Type: Article

References (50)

1. F. H. Westheimer, Science, 1987, 235, 1173.
2. Y. Takagi, Y. Ikeda and K. Taira, Top. Curr. Chem., 2004, 232, 213;
3. D.-M. Zhou and K. Taira, Chem. Rev., 1998, 98, 991;
4. M. Oivanen, S. Kuusela and H. Lönnberg, Chem. Rev., 1998, 98, 961.
5. T. C. Bruice and S. J. Benkovic, in Bio-Organic Mechanisms; ed. W. A. Benjamin, New York, USA, 1966;
6. P. Gillespie, F. Ramirez, I. Ugi and D. Marquarding, Angew. Chem., Int. Ed., 1973, 12, 91.
7. J. R. Cox, Jr and O. B. Ramsday, Chem. Rev., 1964, 64, 317.
8. C. R. Hall and T. D. Inch, Tetrahedron, 1980, 36, 2059.
9. For review see: C. B. Reese, Tetrahedron, 1978, 34, 3143.
10. This type of ambident electrophilicity was published for alkyl aryl phosphates: C. C. P. Wagener, A. M. Modro and T. A. Modro, J. Phys. Org. Chem., 1991, 4, 516.
11. (a) Some examples where acyclic phosphate esters undergo C-O bond scission by water or by using halide ions are reviewed in: C. A. Bunton, Acc. Chem. Res., 1970, 3, 257; note that attack of halide ion on the P atom would lead to the formation of phosphorochloridate and alkoxide;
12. (b) For a rare example using bulky Grignard and lithium reagents (i.e., trityl and mesityl) see: H. Gilman and B. Gaj, J. Am. Chem. Soc., 1960, 82, 6326;
13. (c) For an example using transition metal complexes, see: L. Y. Kuo and N. M. Perera, Inorg. Chem., 2000, 39, 2103.
14. (a) R. V. Hodges, S. A. Sullivan and J. L. Beauchamp, J. Am. Chem. Soc., 1980, 102, 935;
15. (b) R. C. Lum and J. J. Grabowski, J. Am. Chem. Soc., 1992, 114, 8619.
16. N.-Y. Chang and C. Lim, J. Phys. Chem. A, 1997, 101, 8706;
17. G. Menegon, M. Loos and H. Chaimovich, J. Phys. Chem. A, 2002, 106, 9078;
18. G. Menegon Arantes and H. Chaimovich, J. Phys. Chem. A, 2005, 109, 5625.
19. A. Braun and J.-P. Lellouche, Isr. J. Chem., 2001, 41, 329.
20. F. H. Westheimer, Acc. Chem. Res., 1968, 1, 70 and references therein;
21. K. Taira, T. Fanni and D. G. Gorenstein, J. Org. Chem., 1984, 49, 4531 and references therein;
22. G. Aksnes and K. Bergesen, Acta Chem. Scand., 1966, 20, 2508; see also ref. 5.
23. D. G. Gorenstein, Chem. Rev., 1987, 87, 1047 and references therein;
24. A. Dejaegere, X. Liang and M. Karplus, J. Chem. Soc., Faraday Trans., 1994, 90, 1763;
25. G. R. Thatcher and D. R. Cameron, J. Chem. Soc., Perkin Trans. 2, 1996, 767;
26. N.-Y. Chang and C. Lim, J. Am. Chem. Soc., 1998, 120, 2156;
27. C. S. López, O. N. Faza, A. R. de Lera and D. M. York, Chem.-Eur. J., 2005, 11, 2081.
28. P. C. Haake and F. H. Westheimer, J. Am. Chem. Soc., 1961, 83, 1102;
29. R. Kluger, F. Covitz, E. Dennis, L. W. Williams and F. H. Westheimer, J. Am. Chem. Soc., 1969, 91, 6066;
30. R. Kluger and G. R. Thatcher, J. Am Chem. Soc., 1985, 107, 6006;
31. R. Kluger and G. R. Thatcher, J. Org. Chem., 1986, 51, 207.
32. N. Ashkenazi, Y. Karton and Y. Segall, Tetrahedron Lett., 2004, 45, 8003.
33. For review see: F. Eymery, B. Iorga and P. Savignac, Tetrahedron, 1999, 55, 13109.
34. R. G. Pearson and J. Songstad, J. Am. Chem. Soc., 1967, 89, 1827.
35. For other examples using this method see: G. D. Duncan, Z.-M. Li, A. B. Khare and C. E. McKenna, J. Org. Chem., 1995, 60, 7080.
36. This is a highly useful method for derivatization of phosphate di- and mono-esters, widely used for GC determinations. See for example: C. W. Stanley, J. Agric. Food Chem., 1966, 14, 321.
37. +).
38. F. Covitz and F. H. Westheimer, J. Am. Chem. Soc., 1963, 85, 1773.
39. The structure of 4 was proved spectroscopically and chemically by reaction with diazomethane, which quantitatively yielded ethyl (2-t-butyloxy)ethyl methyl phosphate (5) (see supporting information)†.
40. Mesityl Grignard reacted with 1 to yield a 7:1 mixture of both the C-O and the P-O bond cleavage products, respectively.
41. R. G. Pearson, Inorg. Chem., 1988, 27, 734;
42. R. G. Pearson, J. Org. Chem., 1989, 54, 1423.
43. E. C. Ashby, R. Gurumurthy and R. W. Ridlehuber, J. Org. Chem., 1993, 58, 5832.
44. Phosphorus-31 NMR principles and applications, ed. D. G. Gorenstein, Academic Press, Orlando, Florida, USA, 1984.
45. 27 Note that cleaving the exocyclic C-O bond should yield 2-hydroxy-1,3,2-dioxaphospholane 2-oxide and diphenyl ethylphosphine in 1:1 ratio.
46. GAUSSIAN 03 (Revision C.02), Gaussian, Inc., Wallingford, CT, 2004. See ESI†.
47. -1.†
48. M. Cossi, V. Barone, R. Cammi and J. Tomasi, Chem. Phys. Lett., 1996, 255, 327 and references therein.
49. Obviously protonation of anions resulted from OH attack leads to the same product, thus the reaction is thermoneutral for OH attack.
50. According to Table 2 in the gas phase the OH attack occurs exclusively on carbon. For gas phase experiments of analog system resulting in C-O cleavage see ref. 9b.