Cyclization of α,β,ψ,ω-unsaturated bisphosphonates using organolithium-initiated conjugate addition-Michael tandem reaction

Organic Letters

Volumn 1, Issue 9, 1999, Pages 1467-1469

  Nagaoka, Yasuo ^a   Tomioka, Kiyoshi ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001483886     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol991024h     Document Type: Article

References (16)

1. For reviews on alkylphosphonates, see: (a) Engel, R. In Handbook of Organophosphorus Chemistry; Engel, R., Ed.; Marcel Dekker: New York, 1992; Chapter 11.
2. (b) Engel, R. Chem. Rev. 1977, 77, 349-367.
3. (c) Hilderbrand, R. L. The Role of Phosphonates in Living Systems; CRC Press: Boca Raton, FL, 1983.
4. (d) Rodan, G. A. Annu. Rev. Pharmacol. Toxicol. 1998, 38, 375-388.
5. Kelly, S. E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991.
6. Chiral bisphosphine corresponding to (1R,2R)-3b (n = 5, R = H) has been reported in the rhodium-catalyzed asymmetric hydrogenation. Inoguchi, K.; Achiwa, K. Synlett 1991, 49-51.
7. Nagaoka, Y.; Tomioka, K. J. Org. Chem. 1998, 63, 6428-6429.
8. Mizuno, M.; Fujii, K.; Tomioka, K. Angew. Chem., Int. Ed. 1998, 37, 515-517.
9. For the double-Michael reaction of unsaturated carbonyl compounds, see: (a) Bunce, R. A. Tetrahedron 1995, 51, 13103-13159.
10. (b) Uyehara, T.; Shida, N.; Yamamoto, Y. J. Org. Chem. 1992, 57, 3139-3145.
11. Michael addition of lithium enolates to α,β-unsaturated phosphonates has been reported: Darling, S. D.; Muralidharan, F. N.; Muralidharan, V. B. Synth. Commun. 1979, 9, 915-921.
12. Attempted conjugate addition of organolithiums to propenylphosphonate 6 has been reported: Muller E. L.; Modro, T. A. Bull. Soc. Chem. Fr. 1993, 130, 668-672.
13. Deprotonation of phenylethenylphosphonate at the α-position has been reported. Atta, F. M.; Betz, R.; Schmid, B.; Schmidt, R. R. Chem. Ber. 1986, 119, 472-481.
14. 3), 6.81 (1H, ddd, J = 22.3, 4.0, 4.0, H2).
15. An X-ray crystallographic structure of lithium phosphonate has been reported: Denmark, S. E.; Dorow, R. L. J. Am. Chem. Soc. 1990, 112, 2, 864-866.
16. The compound 11 showed a double doublet at δ 3.00 (1H, dd, J = 20.4 (HB-P), 1.0 (HB-H6) Hz) which was assigned as HB7. A peak corresponding to HA (δ 1.85) of trans-3a (n = 6, R = Ph) disappeared, indicating the highly stereoselective deuteration of 10.Compounds 14 and 16 showed the same NMR pattern. The protons HA and HB in trans- and cis-3a were assigned on the basis of the coupling constants which were reasonably simulated by the conformational analysis using MacroModel V6.5.