Six-membered cyclic phosphate–phosphonates: synthesis and stereochemistry of cis/trans-2-phosphorylbenzyloxy-4-aryl-5,5-dimethyl-1,3,2λ⁵-dioxaphosphorinane-2-thiones (selones)

Abstract

A study on the synthesis and stereochemistry of the novel six-membered cyclic phosphate–phosphonates, cis/trans-2-phosphorylbenzyloxy-4-aryl-5,5-dimethyl-1,3,2λ⁵-dioxaphosphorinane-2-thiones (selones) 7a–f has been carried out. The title compounds were obtained in good overall yields by a one-pot procedure using tris(diethylamino)phosphine activated by iodine as the phosphorylating and ring-closing reagent. Their geometric stereoisomers were isolated and characterized. A cis-configuration and a preferred chair conformation of one isomer of 7b have been established by X-ray diffraction analysis. This study also gives a good explanation for the correlation between the configurational assignments and the chemical shifts of C₄-H and ³¹P, which shows some difference from previously reported results.

References

1. (a) A. M. Polozov, A. V. Khotinen and E. N. Klimovitskii, Phosphorus, Sulfur, Silicon Relat. Elem., 1996, 109, 581; (b) D. Bouchu, ibid., 1983, 15, 33; (c) R. L. Shao, G. F. Yang and W. S. Miao, Chem. J. Chin. Univ., 1995, 16, 391.
2. (a) R. S. Edmundson, O. Johnson and D. W. Jones, Phosphorus, Sulfur, Silicon Relat. Elem., 1989, 46, 61; (b) R. S. Edmundson, O. Johnson, D. W. Jones and T. J. King, J. Chem. Soc., Perkin Trans. 2, 1985, 69; (c) O. Johnson, D. W. Jones and R. S. Edmundson, Acta Crystallogr., Sect. C, 1989, 45, 142.
3. J. A. Mosbo and J. G. Verkade, J. Am. Chem. Soc., 1973, 95, 204 and references cited therein.
4. (a) C. Meier, Angew. Chem., Int. Ed. Engl., 1996, 35, 70; (b) M. Sasaki, K. Moriguchi and K. Yanagi, Agric. Biol. Chem., 1988, 52, 159.
5. (a) S. Y. Wu and J. E. Casida, Phosphorus, Sulfur, Silicon Relat. Elem., 1995, 102, 177; (b) C. D. Reddy, M. S. Reddy, S. M. Waidu and K. D. Berlin, ibid., 1995, 102, 103; (c) A. Hirashima, Agric. Biol. Chem., 1989, 53, 175.
6. (a) Y. Nishizuka, Nature, 1984, 308, 693; (b) V. L. Boyd, M. F. Summers, S. M. Ludeman, W. Egan, G. Zon and J. B. Regan, J. Med. Chem., 1987, 30, 366.
7. W. T. Hoeve and H. Wynberg, J. Org. Chem., 1985, 50, 4508.
8. (a) B. Gordillo, C. Garduno, G. Guadarrama and J. Hernandez, J. Org. Chem., 1995, 60, 5180; (b) W. J. Lucas, F. W. Mitchell and C. N. Scully, J. Am. Chem. Soc., 1950, 72, 5491.
9. (a) V. Sum, C. A. Baird, T. P. Kee and M. Thornton-Pett, J. Chem. Soc., Perkin Trans. 1, 1994, 3183; (b) L. Stryer, Biochemistry, Freeman, New York, 3rd edn., 1988.
10. (a) L. Maier and H. Spoerri, Phosphorus, Sulfur, Silicon Relat. Elem., 1992, 70, 39; (b) R. E. Rosen, D. G. Weaver, J. W. Cornille and L. A. Spangler, Eur. Pat. Appl., EP 511 826/ 1992(Chem. Abstr., 1993, 118, 124 779).
11. V. J. Blazis, K. J. Koeller and C. D. Spilling, J. Org. Chem., 1995, 60, 931 and references cited therein.
12. (a) J. Zhou, R. Y. Chen and X. F. Yang, Heteroatom Chem., 1998, 9, 369; (b) J. Zhou and R. Y. Chen, Synth. Commun., 1998, 28 in press.
13. (a) F. Texier-Boullet and A. Foucaud, Synthesis, 1982, 916; (b) R. Engel, Synthesis of Carbon-Phosphorus Bonds, CRC Press, Boca Raton, FL, 1987.
14. (a) R. L. Shao, M. H. Yang and C. X. Zhi, Chin. Chem. Lett., 1993, 4, 767; (b) G. G. David, Non-Biological Aspects of ³¹P NMR Spectroscopy, Pergamon Press, Oxford, 1983, vol. 16; (c) J. Neda, Phosphorus, Sulfur, Silicon Relat. Elem., 1992, 73, 137; (d) S. E. Denmark and R. L. Dorow, J. Org. Chem., 1990, 55, 5926.
15. J. P. Majoral and J. Navech, Bull. Soc. Chim. Fr., 1971, 95, 1331, 2609.
16. C. Stuebe and H. P. Lankelma, J. Am. Chem. Soc., 1956, 78, 976.
17. G. M. Sheldrick, C. Kruger and R. Goddard, SHELXS-86: Crystallographic Computing 3, Oxford University Press, London, 1985.
18. International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4.