Cis-dioxomolybdenum(VI) complexes as new catalysts for the Meyer-Schuster rearrangement

Tetrahedron Letters

Volumn 37, Issue 6, 1996, Pages 853-856

  Lorber, Christian Y ^a   Osborn, John A ^a  

^a UNIVERSITÉ DE STRASBOURG   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; KETONE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030027782     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(95)02324-0     Document Type: Article

References (20)

1. Meyer, K. H.; Schuster, K. Chem. Ber. 1922, 55, 819-823.
2. Parshall, G. W.; Nugent, W. A. Chem. Tech (US) 1988, 376-383 and references therein.
3. Mercier, C.; Chabardès, P. Pure Appl. Chem. 1994, 66, 1509-1518.
4. a) Swaminathan, S.; Narayanan, K. V. Chem.Rev. 1971, 429-438 and references therein.
5. b) Vartayan, S. A.; Babanyan, S. O. Russ.Chem.Rev. 1967, 670-686.
6. c) Heilman, R.; Glenat, R. Ann.Chim. 1963, 8, 175-183.
7. Chabardès, P.; Kuntz, E.; Varagnat, J. Tetrahedron 1977, 33, 1775-1783.
8. a) Pauling, H.; Andrews, D. A.; Hindley, N. C. Helv. Chim. Acta 1976, 59, 1233-1243.
9. b) Olson, G. L.; Cheung, H. C.; Morgan, K. D.; Borer, R.; Saucy, G. Helv. Chim. Acta 1976, 59, 567-585.
10. a) Erman, M. B.; Aul'Chenko, I.S.; Keifits, L. A.; Dulova, V. G.; Novikov, J. N.; Vol'Pin, M. E. Tetrahedron Lett. 1976, 34, 2981-2984.
11. b) Erman, M. B.; Gulyi, S. E.; Aul'Chenko, I. S. Mendeleev Commun. 1994, 89-89.
12. a) Narasaka, K.; Husama, H.; Hayashi, Y. Chem. Lett. 1991, 1413-1416.
13. b) Yamano, Y.; Tobe, C.; Ito, M. J. Chem. Soc., Perkin Trans.1 1995, 1895-1904.
14. Lorber, C. Y. Thesis Université Louis Pasteur de Strasbourg 1995.
15. Chabardès, P. Tetrahedron Lett. 1988, 29, 6253-6256.
16. Lorber, C. Y.; Youinou M. T. Y.; Osborn, J. A. to be published.
17. 2 (0.119 mmol), 200 mg of 2-methyl-3-butyn-2-ol (2.377 mmol), 772 mg of dibutylsulfoxide (4.754 mmol), 156 mg of 4-tert-butyl-benzoic acid (0.594 mmol), 150 mg of n-nonane (internal standard, 1.190 mmol) and 2 g of 1,2-dichlorobenzene (solvent) were placed in a screw caps vial and heated to 100°C under stirring. After 5 hours, the yield and selectivity were determined by gas chromatography (chromatograph: HP 5890 II; column: HP-1, methylsilicon gum, 10 m x 0.53 mm x 2.65 μm; detector: FID): yield in prenal 90% (recovered alcohol: 9%). After 10 hours, the conversion is complete: yield in prenal 98%.
18. Lorber, C. Y.; Osborn, J. A. to be published.
19. Nota: X = OR, C1, 1/2 acac, ... Sulfoxide ligands probably bound to molybdenum center are not represented in this scheme.
20. In the absence of promoter, the isomerisation is only stoichiometric, and a fraction of the propargylic alcohol is dehydrated into enyne.