Synthesis of 3-chloro-Δ3-cephem-4-carboxylate by addition/cyclization of allenecarboxylate. Copper(II)-promoted aerobic oxidation of arenesulfinic acids

Bulletin of the Chemical Society of Japan

Volumn 69, Issue 5, 1996, Pages 1391-1396

  Tanaka, Hideo ^a   Kikuchi, Ryo ^a   Torii, Sigeru ^a  

^a OKAYAMA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CEPHEM DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; REACTION ANALYSIS;

EID: 0029944259     PISSN: 00092673     EISSN: None     Source Type: Journal    
DOI: 10.1246/bcsj.69.1391     Document Type: Article

References (30)

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16. 3-cephem-4-carboxylate 4 followed by elimination of chloride anion is an alternative route to 3. However, the addition/elimination reaction seems not to occur under these conditions since most of 4 was recovered upon treatment of 4 with sodium benzenesulfinate (0.5 molar amount) in NMP (20-22 °C, 4 h).
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18. a) Sodium benzenesulfonate (8a): "Beilsteins Handbuch der Organischen Chemie," ed by B. Prager, P. Jacobson, P. Schmidt, and D. Stern, Verlag von Julius Springer, Berlin (1928), Band 11, p. 26
19. b) Sodium p-toluenesulfonate (8c): "Beilsteins Handbuch der Organischen Chemie," ed by B. Prager, P. Jacobson, P. Schmidt, and D. Stern, Verlag von Julius Springer, Berlin (1928), Band 11, p. 97
20. c) Sodium p-chlorobenzenesulfonate (8d) and sodium p-bromobenzenesulfonate (8, X=Br, M=Na): R. R. Baxter and F. D. Chattaway, J. Chem. Soc., 107, 1815 (1915)
21. 2, M=Na): "Beilsteins Handbuch der Organischen Chemie," ed by B. Prager, P. Jacobson, P. Schmidt, and D. Stern, Verlag von Julius Springer, Berlin (1928), Band 11, p. 67.
22. K. K. Andersen, "Sulphinic Acids and Their Derivatives," in "Comprehensive Organic Chemistry," Vol. 3, ed by D. N. Jones, Pergamon Press, Oxford (1979), Chap. 11.18, pp. 317-329, and the references cited therein.
23. The HPLC analysis of the reaction mixture on the course of the aerobic oxidation showed that the oxidation of the benzenesulfinate 7a smoothly proceeded to give the sulfonate Sa in 83% yield within only 5 min.
24. The yield of sodium benzenesulfonate Sa under argon atmosphere were linearly increased as the increase of the amount of copper(II) chloride up to 0.5 molar amount; namely, oxidation of sodium benzenesulfinate 7a with 0.5 molar amount of copper(II) chloride gave 8a in 47% yield (recovery of 7a: 46%). However, a larger amount of copper(II) chloride, more than 1 molar amount, did not efficiently work since less than 57% yield of Sa was obtained.
25. 2O.
26. A similar aerobic oxidation of p-toluenesulfinic acid in the presence of copper(II) acetylacetonate and tetrabutylammonium chloride in acetonitrile was reported: H. Bredereck, A. Wagner, R. Blaschke, G. Demetriades, and K.-G. Kottenhahn, Chem. Ber., 92, 2628 (1959).
27. 1HNMR, and the isolation experiments.
28. The reaction of the allenecarboxylate 2 with increased amounts of copper(II) chloride (1 molar amount) under argon atmosphere could completely remove the formation of 3 but did not improve the yield of 4 (42%).
29. 3, was efficiently formed.
30. It can not be ruled out that active oxygen species, generated from molecular oxygen in the aerobic media involving Cu(II) catalysts, work, in part, as an oxidant for the transformation of the sulfinate anion into the sulfonate anion.