Abstract
This chapter summarizes some of the most characteristic results obtained with the use of mainly homogeneous metal complex catalysts either in the industry or in processes recommended for practical use. These are large scale processes of asymmetric synthesis of the herbicide metolachlor, synthesis of optically pure menthol with the use of chiral iridium and rhodium phosphine complexes, consideration of the synthesis of ethyl 2-hydroxybutyrate as a monomer for the preparation of biodegradable polyesters with use of heterogeneous chiral modified nickel catalyst, the manufacturing of (R)-pantolactone by means of a possible catalytic systems for enantioselective hydrogenation of ketopantolactone, and catalytic systems for the preparation of other pharmaceuticals.
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Keywords
- Asymmetric Synthesis
- Ethyl Pyruvate
- Chiral Ligand
- Asymmetric Hydrogenation
- Enantioselective Hydrogenation
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
References
a) Knowles, W.S, Sabacky, M.J. and Vineyard, B.D. (1972) Catalytic asymmetric hydrogenation, J. Chem. Soc., Chem. Commun. 10–11. b) Knowles, W.S. (1986) Application of organometallic catalysis to the commercial production of L-DOPA, J. Chem. Ed., 63, 222–225. c) Chirality in industry (1992) Collins, A.N., Sheldrake, G.N., and Crosby, J. (eds.), Wiley, N.Y., V.I. 409 pp. d) Chirality in industry (1997) Collins, A.N., Sheldrake, G.N., and Crosby, J. (eds), Wiley, N.Y., V.II. 418 pp.
Kagan, H.B. (1988) Asymmetrric catalysis in organic synthesis with industrial perspectives, Bull. Soc. Chim. Fr., N 5, 846–853.
Karpeiskaya, E.I., Levitina, E.S., Godunova, L.F. and Klabunovskii, E.I. (1986) Reaction of catalytic enantioselective aminolysis of delta-2-oxazolin-5-ones as a method of asymmetric synthesis of alpha-amino acids, J. Mol. Catal. A: Chem. 34, 129–143.
Tani, K., Yamagata, T., Akutagawa, S., Kumobayashi, H., Taketomi, T., Takaya, H., Miyashita, A., Noyori, R. and Otsuka, S. (1984) Highly enantioselective isomerization of prochiral allylamines catalysed by chiral diphosphine Rh (I) complexes. Preparation of optically active enamines, J. Amer. Chem. Soc. 106, 5208–5217.
a) Cullen, W.R., Frizuk, M.D., James, B.R., Kutney, J.P., Kang, G.J., Herb, G., Thorburn, J.S. and Spogliarich, R.S. (1990) Asymmetric homogeneous hydrogenation of imines using Rh-phosphine systems, J. Mol. Catal. A. Chem. 62, 243–253. b) Moser, H., Rihs, G. and Sauter, H (Ciba-Geigy Co.) (1982) Der Einfluss von Atropoisomerie und chiralen Zentrum auf die biologische Aktivitaet des Metolachlor, Z. Natuforschung 37b, 451–462.
a) Spindler, F., Pugin, B., and Blaser, H.U. (1990) Novel diphosphinoiridium catalyst for the enantioselective hydrogenation of N-arylketimines, Angew. Chem. Int. Ed. Engl., 29, 558–559. b) Spindler, F., Pugin, B., Jalett, H.-P., Buser, H.P., Pittelkow, U. and Blaser, H.U. (1996) A technically useful catalyst for the homogeneous enantioselective hydrogenation of N-arylimines: a case study, Chemistry Industry (Catalysis of Organic Reactions), (Dekker) 68, 153–166.
Bader, H.B. and Blaser, H.U. (1997) Catalysis for agrochemicals: the case history of the DUAL Herbicide, Stud. Surf. Sci. Catal., 108, 17–29.
Togni, A., Breutel, C., Schnyder, A., Spindler, F., Landert, H. and Tijani, A. (1994) A novel easily accessible chiral ferrocenyl diphosphine for highly enantioselective hydroganation, allylic alkylation and hydroboration reactions, J. Amer. Chem. Soc., 116, 4062–4066.
Zhorov, E.Yu., Pavlov, V.A., Fedotova, O.A., Shvedov, V.I., Mistryukov, E.A., Platonov, D.N., Gorshkova, L.S. and Klabunovskii, E.I. (1991) Enantioselective metal-complex catalysis, Comm. 7., Asymmetric hydrosilylation of imines and oximes on catalyst [Rh(COD)Cl]2 (S)-Phephos, Izv. AN SSSR. Ser. Khim., 865–868.
Joo, F., and Katho, A. (2004) Hydrogenation, in Aqueous Phase Organometallic Catalysis, Herrmann, W.A. (ed.), Wiley-VCH, Weinheim, 2nd ed., 429–463.
Amrani, Y., Lecomte, L., and Sinou, D. (1989) Chiral sulfonated phosphines, syntheses and use as ligands in asymmetric hydrogenation using an aqueous-organic two phase solvent system, Organometallics, 8, 542–547.
Tas, D., Rane, V.H., Parton, R.F. and Jacobs, P.A (1997) Immobilized Noyori catalyst on beta-zeolite in hydrogenation of beta-ketoester, 15th North American Catalysis Society Meeting, Chicago, IL. Abstracts.
a) Wan, K.-T. and Davis, M.E. (1995) Asymmetric synthesis of naproxen by a new heterogeneous catalyst, J. Catal. 152, 25–30. b) Davis, M.E. and Wan, K.-T. (1997) A route to the rational design of heterogeneous catalysts, in “The Robert A. Welch Foundation Conference on Chemical Research. XXXX. Chemistry on the Nanometer Scale”. Houston, 21 Oct. 1996, pp. 1–13.
a) Wan, K.-T. and Davis, M.E. (1994) Design and synthesis of a heterogeneous asymmetric catalysts, Nature, 370, 449–450 b) Wan, K.-T. and Davis, M.E. (1993) Asymmetric hydrogenation in water by a Rhodium complex of sulfonated 2,2-bis(diphenylphosphine)-1,1-binaphthyl (BINAP), J. Chem. Soc., Chem. Comm. 1262–1264.
Ohta, T., Miyake, T. and Takaya, H. (1992) An efficient synthesis of optically active methyloxetan-2-one: asymmetric hydrogenation of diketene catalysed by BINAP-Ru complexes, J. Chem. Soc., Chem. Comm. 1725–1726.
Chiellini, E. and Solaro, R. (1996) Biodegradable polymeric materials, Adv. Mater., 8, 305; Chem. Abstr. 1996, 125, 60185.
a) Sheldon, R.A. (1993) Chirotechnology. Industrial synthesis of optically active compounds, Marcel Dekker Inc., N.Y., Basel, Hong Kong, 423 pp. b) Klabunovskii, E.I. (1996) Catalytic asymmetric synthesis of beta-hydroxyacids and their esters, Russian Chem. Rev. 65, 329–344 c) Merck Co. Inc., SU 1287756.A3. KRKA, SU 1757471.A3.
Vankelecom, I.F.J., Tas, D., Parton, R.F., Van de Vyver, V. and Jacobs, P.A. (1996) Chiral catalytic membranes, Angew. Chem. Int. Ed. Engl. 35, 1346–1348.
Ojima, I., Kogure, T. and Achiwa, K. (1977) Effective homogeneous hydrogenation of alpha-ketoesters catalysed by neutral phosphine ligands and application to the asymmetric synthesis of lactates, J. Chem. Soc., Chem. Comm. 428–430.
Spindler, F., Pittelkow, U. and Blaser, H.U. (1991) A highly enantioselective Rh-catalyst for the hydrogenation of aliphatic alpha-keto esters, Chirality, 3, 370–375.
a) Blaser, H.U. and Jalett, H.-P. (1993) Enantioselective hydrogenation of alpha-ketoacids using Pt-catalysts modified with cinchona alkaloids, Stud. Surf. Sci. Catal., 78, 139–146. b) Baiker, A. (1999) Supercritical fluids in heterogeneous catalysis, Chem. Rev. 99, 453–473.
Hoffmann-La Roche, US 3.884.966, 20.05.1975, Chem. Abstr. 84, 16758 (1976)
Ojima, I. (1984) Homogeneous asymmetric catalysis by means of chiral rhodium complexes, Pure Appl. Chem., 56, 99–110.
Achiwa, K., Kogure, T. and Ojima, I. (1977) Catalytic asymmetric synthesis of R(-)- and (S)-(+)-pantolactone, Tetrahedron Lett., 4431–4432.
Achiwa, K., Kogure, T. and Ojima, I. (1978) Highly effective catalytic asymmetric synthesis of (R)-(-)-pantolactone, Chem. Lett. 297–298.
Ojima, I., Kogure, T. and Terasaki, S. (1978) Effective biomimetic route to D-(+)-pantothenate using asymmetric hydrogenation catalyzed by a chiral Rh complex in the key steps, J. Org. Chem. 43, 3444–3446.
Ojima, I., and Kogure, T. (1980) The asymmetric hydrogenation of alphaketo esters catalyzed by Rh complexes with chiral diphosphine ligands. On the catalytic cycles and the mechanism of asymmetric induction, J. Organomet. Chem., 195, 239–248.
Weishaeupl, J. (1984) DIOP als Ligand in der asymmetrischen Katalyse mit Uebergangsmetall-Phosphin-Komplexen, Oesterreichische Chemie-Zeitschrift 85, H 1, 1–5.
Kagan, H.B. (1982) Asymmetric synthesis using organometallic catalysis, in Wilkinson G. (ed.) Comprehensive organometallic chemistry, Pergamon Press, Oxford, 8, 463–498.
Yamamoto, K. and Saeed-ur-Rahman (1984) New entry to the preparation of chiral bis(dicyclohexylphosphino)alkane derivatives. Use for Rh-catalyzed hydrogenation of carbonyl compounds, Chem. Lett. 1603–1606.
Takahashi, H., Hattori, M., Chiba, M., Morimoto, T. and Achiwa, K. (1986) Preparation of new chiral pyrrolidinebisphosphines as highly effective ligands for catalytic asymmetric synthesis of (R)-(-)- pantolactone, Tetrahedron Lett., 27, 4477–4480.
Morimoto, T., Takahashi, H., Fujii, K., Chiba, M. and Achiwa, K. (1986) Synthesis of a new chiral pyrrolidine ligand bearing two different types of phosphino groups and their effects on the asymmetric hydrogenation of ketopantolactone, Chem. Lett., 2061–2064.
Tani, K., Suwa, K., Tanigawa, E., Ise, T., Yamagata, T., Tatsuno, Y., and Otsuka, S. (1989) Preparation of optically active peralkyldiphosphines and their use, as the Rh complex, in the asymmetric catalytic hydrogenation of ketones, J. Organomet. Chem. 370, 203–221.
Hatat, C., Karim, A., Kokel, N., Mortreux, A. and Petit, F. (1990) Hydrogenation asymetrique de cetones activees par des complexes rhodium alkyl-AMPP: optimisation et etude du mechanisme, New J. Chem. 14, 141–152.
Roucoux, A., Agboussou, F., Mortreux, A. and Petit, F. (1993) New alkylarylamido phosphine phosphinites as chiral diphosphines for asymmetric hydrogenation of acilated keto compounds, Tetrahedron Asymm. 4, 2279–2282.
Schrock, R.R., and Osborn, J.A. (1970) Rhodium catalysts for the homogeneous hydrogenation of ketones, J. Chem. Soc., Chem. Comm. 667–668.
Brunner, H., and Tracht, T. (1998) Asymmetric catalysis. 128. Diastereomeric Rh(I) complexes in the enantioselective hydrogenation of ketopantolactone, Tetrahedron Asymm. 9, 3773–3780.
Shimizu, S., Hata, H., and Yamada, H. (1984) Reduction of ketopantolactone to D-(-) pantolactone by microorganisms, Agr. Biol. Chem. 48, 2285–2291.
Matteoli, U., Beghetto, V. and Serivanti, A. (1999) Asymmetric hydrogenation by an in situ prepared (S)-BINAP-Ru(II) catalytic system, J. Mol. Catal. A. Chem. 140, 131–137.
Wolfson, A., Vankelekom, I.F.J., Geresh, S. and Jacobs, P.A. (2003) The role of the solvent in the asymmetric hydrogenation of beta-keto esters with Ru-BINAP, J. Mol. Catal. A. Chem. 198, 39–45.
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KLABUNOVSKII, E., SMITH, G.V., ZSIGMOND, Á. (2006). PRACTICAL ASYMMETRIC CATALYTIC REACTIONS. In: KLABUNOVSKII, E., SMITH, G.V., ZSIGMOND, Á. (eds) HETEROGENEOUS ENANTIOSELECTIVE HYDROGENATION. Catalysis by Metal Complexes, vol 31. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-4296-6_7
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