Selective manganese-mediated transformations using the combination: KMnO4/Me3SiCl

Tetrahedron Letters

Volumn 38, Issue 13, 1997, Pages 2339-2342

  Markó, István E ^a   Richardson, Paul R ^a   Bailey, Mark ^a   Maguire, Anita R ^b   Coughlan, Niall ^b  

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

^b UNIVERSITY COLLEGE CORK   (Ireland)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ORGANOCHLORINE DERIVATIVE; SULFOXIDE;

ARTICLE; CHLORINATION; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; OXIDATION; REACTION ANALYSIS;

EID: 0031592567     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00309-2     Document Type: Article

References (19)

1. 1. (a) Markó, I.E., Richardson, P.F. Tetrahedron Lett., 1991, 32, 1831;
2. (b) Richardson, P.F., Markó, I.E. Synlett, 1991, 733;
3. (c) Bellesia, F., Ghelfi, F., Pagnoni, U.M., Pinetti, A. J. Chem. Res.(S), 1989, 108;
4. (d) Bellesia, F., Ghelfi, F., Pagnoni, U.M., Pinetti, A. J. Chem. Res.(S), 1989, 360; Bellesia, F., Ghelfi, F., Pagnoni, U.M., Pinetti, A. J. Chem. Res.(S), 1990, 188.
5. (d) Bellesia, F., Ghelfi, F., Pagnoni, U.M., Pinetti, A. J. Chem. Res.(S), 1989, 360; Bellesia, F., Ghelfi, F., Pagnoni, U.M., Pinetti, A. J. Chem. Res.(S), 1990, 188.
6. 2. The manganese complex generated under these conditions is thermally sensitive and decomposes at temperatures above -35°C. Strict control of temperature and additives is necessary to ensure good yields.
7. 2COCl. In these cases, although some dichlorination took place, the desired dihalides were contaminated by numerous other by-products.
8. 4. In some cases, the initial green colour of the reaction mixture discharged at the end of the reaction. A slight excess of the complex leads to a greenish solution, even after complete consumption of the alkene reagent.
9. 5. The anti-stereochemistry has been established by comparison with authentic samples and by X-ray crystallographic analysis. The mixture of syn/anti isomers obtained for aromatic substituted alkenes probably originates from a competitive solvolysis of the intermediate manganese complex leading to an ionpair which rapidly recombines with chloride ion.
10. 6. Beside the observed dichlorides, the bicyclic ethers 9 and 10 are produced in about 30% yield by intramolecular interception of the organomanganese intermediate by the closely located epoxide. (equation presented)
11. 7. For opening of epoxides, see for example: (a) Andrews, G.C.; Crawford, T.C.; Contillo, L.G. Tetrahedron Lett., 1981, 22, 3803;
12. (b) Martinez, L.E.; Leighton, J.L.; Carsten, D.H.; Jacobsen, E.N. J. Am. Chem. Soc., 1995, 117, 5897;
13. (c) Leighton, J.L.; Jacobsen, E.N. J. Org. Chem., 1996, 61, 389.
14. 8. For chemoselective oxidation of sulfides into sulfoxides, see for example: (a) Reich, H.J.; Chow, F.; Peake, S.L. Synthesis, 1978, 299;
15. (b) Edwards, M.P.; Ley, S.V.; Lister, S.G.; Palmer, B.D.; Williams, D.J. J. Org. Chem., 1984, 49, 3503;
16. (c) Hudlicky, M. Oxidations in Organic Chemistry, American Chemical Society, Washington, 1995;
17. (d) Di Furia, F.; Licini, G.; Modena, G.; Motterle, R.; Nugent, W.A. J. Org. Chem., 1996, 61, 5175 and references cited therein.
18. 3 as the active species and seem to favour either the Mn(VII) oxo derivative 11 or the hypochloride 12. Further work is however needed to fully ascertain the stucture of the reactive complex. (equation presented)
19. 4 and the solvent evaporated in vacuo giving the product (556 mg; 94%) as a clear oil.