Abstract
Selective reactions of terpenes, catalyzed by different heterogeneous systems, are reported. α-pinene and limonene epoxides can be effectively isomerized to carbonyl compounds (selectivity >70%) over silica aluminas that appear to be good alternatives to homogeneous ZnBr2. The different reactivity of geometric isomers can be used to separate them. Unsaturated ketones can be converted through a two-step one-pot reaction in cyclic or bicyclic ethers through a bifunctional process involving a hydrogenation and an acid-catalyzed step. However, the choice of the solvent allows to inhibit the acidic sites, thus obtaining a selective hydrogenation reaction. On the other hand, the acidic reaction alone can be useful for alcohol epimerization and epimer separation. Grafting of Ti in a siliceous matrix gives rise to a material with both redox and acidic properties. Solids obtained in this way are active and selective in the epoxidation of terpenic alcohols but can also promote bifunctional reactions.
Similar content being viewed by others
References
K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavours Materials (Wiley-VCH, New York, 1997).
H. Mimoun, Chimia 50 (1996) 620.
K. Arata and K. Tanabe, Chem. Lett. (1979) 1017.
J. Kaminska, M.A. Schwegler, A.J. Hoefnagel and H. van Bekkum, Recl. Trav. Chim. Pays-Bas 111 (1992) 432.
A.T. Liebens, C. Mahaim and W.F. Holderich, Stud. Surf. Sci. Catal. 108 (1997) 587.
P.J. Kunkeler, J.C. van der Waal, J. Bremmer, B.J. Zuurdeeg, R.S. Downing and H. van Bekkum, Catal. Lett. 53 (1998) 135.
J.L. Flores Moreno, L. Barakat and F. Figueras, Catal. Lett. 77 (2001) 113.
N. Ravasio, M. Finiguerra, M. Gargano, Chem. Ind. Series, Catalysis of Organic Reactions, F.E. Herkes (ed.) (Marcel Dekker, New York, 1998) p. 513.
G. Ramis, L. Yi, G. Busca and N. Ravasio, II Conv. Sc. Cons. Chim. Mater., Firenze (I), 13–15 Feb. 1995, Book of Abstracts, C23.
R.L. Settine, G.L. Parks and G.L.K. Hunter, J. Org. Chem. 29 (1964) 616.
K. Arata, S. Akutagawa and K. Tanabe, J. Catal. 41 (1976) 173.
F. Zaccheria, R. Psaro, N. Ravasio and L. De Gioia, Chem. Ind. Series, Catalysis of Organic Reactions, M. Ford (ed.) (Marcel Dekker, New York, 2001) p. 601.
L. Salles, A.F. Nixon, N.C. Russell, R. Clarke, P. Pogorzelec and D.J. Cole-Hamilton, Tetrahedron: Asymmetry 10 (1999) 1471.
W. Chrisman, J.N. Camara, K. Marcellini, B. Singaram, C.T. Goralski, D.L. Hasha, P.R. Rudolf, L.W. Nicholson and K.K. Borodychuk, Tetrahedron Lett. 42 (2001) 5805.
E.E. Royals and L.L. Harrell, J. Am. Chem. Soc. 77 (1955) 3405.
Y. Fujiwara, N. Masato and K. Igawa, JP 85-253708 to Toyo Soda.
N. Ravasio, M. Antenori, M. Gargano and P. Mastrorilli, Tetrahedron Lett. 37 (1996) 3529.
K.H. Schulte-Elte, P. Fankhauser and G. Ohloff, JP 77-124356 to Firmenich.
H. Masuda and S. Mihara, JP 84-155438 to Ogawa and Co.
C. Chapuis and D. Jacoby, Appl. Catal. A 221 (2001) 93.
J-j. Young, L-j. Jung and K-m. Cheng, Tetrahedron Lett. 41 (2000) 3415.
N. Ravasio, V. Leo, F. Babudri and M. Gargano, Tetrahedron Lett. 38 (1997) 7103.
F. Boccuzzi, A. Chiorino, M. Gargano and N. Ravasio, J. Catal. 165 (1997) 140.
F. Boccuzzi, A. Chiorino, G. Martra, M. Gargano, N. Ravasio and B. Carrozzini, J. Catal. 165 (1997) 129.
F. Boccuzzi, S. Coluccia, G. Martra and N. Ravasio, J. Catal. 184 (1999) 316.
F. Zaccheria, R. Psaro, N. Ravasio, Recent Research and Developments in Catalysis, G. Pandalai (ed.) (Research Signpost, Trivandrum) 2 (2003) 23.
G. Ohloff, W. Giersch, K.H. Schulte-Elte and C. Vial, Helv. Chim. Acta 59 (1976) 1140.
H. Masuda and S. Mihara, JP 85 65,879 to Ogawa and Co.
N. Ravasio, R. Psaro, F. Zaccheria and S. Recchia, Chem. Ind. Series, Catalysis of Organic Reactions, D. Morrel (ed.) (Marcel Dekker, New York, 2003) p. 263.
P. Linares, S. Salido, J. Altarejos, M. Nogueras and A. Sanchez, Flavour and Fragrance Chemistry, V. Lanzotti and O. Tagliatela Scafati (eds) (Kluwer Ac. Publ., Dordrecht, 2000) p.101.
H. Mimoun, U.S. Patent 6,245,952 to Firmenich SA (2001).
N. Ravasio, N. Poli, R. Psaro, M. Saba and F. Zaccheria, Top. Catal. 13 (2000) 195.
T. Maschmeyer, F. Rey, G. Sankar and J.M. Thomas, Nature 378 (1995) 159.
C. Berlini, M. Guidotti, G. Moretti, R. Psaro and N. Ravasio, Catal. Today 60 (2000) 219.
A. Bhaumik and T. Tatsumi, J. Catal. 182 (1999) 349.
J.C. van der Waal, P. Lin, M.S. Rigutto and H. van Bekkum, Stud. Surf. Sci. Catal. 105 (1997) 1093.
J.C. van der Waal, P. Lin, M.S. Rigutto and H. van Bekkum, Appl. Catal. A: Gen. 167 (1998) 331.
M. Guidotti, N. Ravasio, R. Psaro, G. Ferraris and G. Moretti, J. Catal. 214 (2003) 247.
J. Shabtai, R. Lazar and E. Biron, J. Mol. Catal. 27 (1984) 35.
M. Fuentes, J. Magraner, C. De Las Pozas, R. Roque-Malherbe, J. Perez Pariente and A. Corma, Appl. Catal. 47 (1989) 367.
N. Ravasio, M. Antenori, F. Babudri and M. Gargano, Stud. Surf. Sci. Catal. 108 (1997) 625.
M. Guidotti, R. Psaro and N. Ravasio, Chem. Commun. (2000) 1789.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ravasio, N., Zaccheria, F., Guidotti, M. et al. Mono- and Bifunctional Heterogeneous Catalytic Transformation of Terpenes and Terpenoids. Topics in Catalysis 27, 157–168 (2004). https://doi.org/10.1023/B:TOCA.0000013550.28170.6a
Issue Date:
DOI: https://doi.org/10.1023/B:TOCA.0000013550.28170.6a