The Role of Alkali and Alkaline Earth Metal Ions on the Hydrolysis of 2-Ferrocenyl-1,3-dioxane in Acetonitrile Solutions

• Autorzy: Navarro, E. , González, F. , Astudillo, P. , Vázquez-Hernández, M. , Hernández-Rodríguez, M. , Juaristi, E.
• Języki publikacji: EN

Abstrakty

EN

he hydrolysis of 2-ferrocenyl-1,3-dioxane in the presence of different alkali (Li+, Na+, K+ ), alkaline earth (Mg2+, Ca2+ ), and transition metal ions (Zn2+) was studied in acetonitrile solutions. The evolution of the hydrolysis of the dioxane ketalmoiety and the formation of the reaction products was monitored by analysis of the electrochemical oxidation potential of the ferrocenyl redox centre, which maintains its integrity in the reaction and facilitates the determination of the concentrations of both the starting material and products. It was found that only Ca2+ promotes the hydrolysis of 2-ferrocenyl- 1,3-dioxane to produce ferrocenecarboxaldehyde and 1,3-propanediol in up to quantitative yield when an excess of the Ca2+ metal ion is present. Theoretical calculations (B3LYP/3-21G*) led to a proposal for the hydrolysis mechanism, in which coordination of solvated calcium to theO–C–O dioxane segment is determinant for the process to begin.

Słowa kluczowe

EN

ferrocenyldioxane; hydrolysis; salt effects; stereoelectronic interactions; metal ions; DFT calculations

• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2007
• Tom: Vol. 81, nr 5-6
• Strony: 921-930
• Opis fizyczny: Bibliogr. 20 poz., rys.

Twórcy

autor

Navarro, E.

autor

González, F.

autor

Astudillo, P.

autor

Vázquez-Hernández, M.

autor

Hernández-Rodríguez, M.

autor

Juaristi, E.

• Departamento de Química, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Apartado Postal 14-740, 07000-México D. F., Mexico,

Bibliografia

• 1. Greene T.W. and Wuts P.G.M., Protective Groups in Organie Synthesis 3rd ed., John Wiley & Sons, New York 1999, p. 297.
• 2. Wenkert E. and Goodwin T.E., Synth. Comm., 7,409 (1977).
• 3. Ellison R.A., Lukenbach E.R. and Chiu C.-W., Tetrahedron Lett., 499 (1975).
• 4. Colvin E.W., Raphael R.A. and Roberts J.S., J. Chem. Soc. Chem. Commun., 858 (1971).
• 5. Lipshutz B.H and Harvey D.F., Synth. Comm., 12, 267 (1982).
• 6. Bonin M., Royer J., Grierson D.S. and Husson H.-P., Tetrahedron Lett., 27, 1569 (1986).
• 7. Roush W.R. and Sciotii R.J, J. Am. Chem. Soc., 116, 6457 (1994).
• 8. Sen S.E., Roach S.L., Boggs J.K., Ewing G.J. and Magrath J., J. Org. Chem., 62, 6684 (1997).
• 9. Jin T.-S., Ma Y.-R., Zhang Z.-H. and Li T.-S., Org. Prep. Proceed. Int., 30, 463 (1998).
• 10. Marcantoni E., Nobili R, Bartoli G., Bosco M. and Sambri L., J. Org. Chem., 62, 4183 (1997).
• 11. Ford K.L. and Roskamp EJ., Tetrahedron Lett., 33, 1135 (1992).
• 12. Juaristi E., Rosquete-Pina G.A., Vazquez-Hernandez M. and Mota A.J., Pure Appl. Chem., 75, 589 (2003).
• 13. Vazquez-Hernandez M., Rosquete-Pina G.A. and Juaristi E., J. Org. Chem., 69, 9063 (2004).
• 14. Jurgen H., Angew. Chem. Int. Ed. Engl, 23, 831 (1984).
• 15. Salas M., Gordillo B. and Gonzalez F.J., J. Electroanal. Chem., 574, 33 (2004).
• 16. Steffen W., Laskoski M., Collins G. and Bunz U.H.F., J. Organomet. Chem., 630, 132 (2001).
• 17. Ion L, Moutet J.-C., Popescu A., Saint-Aman E., Tomaszewski L. and Gautier-Luneau L, J. Electroanal. Chem., 440, 145(1997).
• 18. Frisch M.J., Trucks G.W., Schlegel H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., Montgomery Jr. J.A., Vreven T., Kudin K.N., Burant J.C., Millam J.M., lyengar S.S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G.A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J.E.,Hratchian H.P., Cross J.B., Adamo C., Jaramillo J., Gomperts R., Stratmann R.E., Yazyev O., Austin A.J., Cammi R., Pomelli C., Ochterski J.W., Ayala P.Y, Morokuma K., Voth G.A., Salvador R, Dannenberg J.J., Zakrzewski V.G., Dapprich S., Daniels A.D., Strain M.C., Farkas O., Malick D.K., Rabuck A.D., Raghavachari K., Foresman J.B., Ortiz J.V., Cui Q., Baboul A.G., Clifford S., Cioslowski J., Stefanov B.B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R.L., Fox D.J., Keith T., Al-Laham M.A., Peng C.Y., Nanayakkara A., Challacombe M., Gill RM.W., Johnson B., Chen W., Wong M.W., Gonzalez C. And Pople J.A., Gaussian 03, Revision C.02, Gaussian, Inc., Walingford CT, 2004.
• 19. (a) Loupy A., Tchoubar B. And Astruc D., Chem. Rev., 92,1141 (1992); (b) Seebach D., Beck A.K. and Studer A., Modem Synthetic Methods 1995, VCH: Weinheim, 1995; pp. 1-178.
• 20. Juaristi E. And Cuevas G., The Anomeric Effect, CRC Press: Boca Raton, FL (1995).