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Catalytic racemisation of chiral amines and application in dynamic kinetic resolution

Blacker, A. John, Stirling, Matthew J. and Page, Michael I. (2007) Catalytic racemisation of chiral amines and application in dynamic kinetic resolution. Organic Process Research and Development, 11 (3). pp. 642-648. ISSN 1083-6160

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A mild and efficient procedure for the racemisation of optically active amines has been developed and applied to the dynamic kinetic resolution (DKR) of a racemic amine. Pentamethylcyclopentadienyliridium (III) iodide dimer dissolved in a convenient solvent is the precatalyst that reacts in situ with primary, secondary, or tertiary amines to form what we have named a SCRAM catalyst. This is able to dehydrogenate a substrate amine to form an imine, which, depending upon the reaction conditions, is then reduced back to the amine. When an optically active amine is mixed with the iridium precatalyst, racemisation is observed. The SCRAM catalyst is used under mild conditions compatible with suitable enzymes and acyl donors, and thus the DKR of an amine has been effected, giving significantly higher yield than if the enzyme alone was used. A mixed carbonate was identified as the optimal acyl donor, giving a carbamate product that is readily removed by acidic hydrolysis

Item Type: Article
Subjects: Q Science > Q Science (General)
Q Science > QD Chemistry
Schools: School of Applied Sciences
School of Applied Sciences > Biomolecular Sciences Research Centre
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References: (1) Coppola, G. M.; Schuster, H. F. Asymmetric Synthesis. Construction of Chiral Molecules Using Amino Acids; Wiley-Interscience: New York, 1987. (2) Procter, G. Asymmetric Synthesis; Oxford University Press: Oxford, 1996. (3) Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds. ComprehensiVe Asymmetric Catalysis; Springer: Berlin; London, 1999. (4) Blaser, H. U.; Schmidt, E. D. Asymmetric Catalysis on Industrial Scale: Challenges, Approaches and Solutions; Wiley-VCH: Chichester; John Wiley [distributor]: Weinheim, 2004. (5) Fogassy, E.; Nogradi, M.; Kozma, D.; Egri, G.; Palovics, E.; Kiss, V. Org. Biomol. Chem. 2006, 4 (16), 3011-3030. (6) Sheldon, R. A. J. Chem. Technol. Biotechnol. 1996, 67 (1), 1-14. (7) Koh, J. H.; Jeong, H. M.; Park, J. Tetrahedron Lett. 1998, 39 (31), 5545- 5548. (8) Csjernyik, G.; Bogar, K.; Backvall, J. E. Tetrahedron Lett. 2004, 45 (36), 6799-6802. (9) Ito, M.; Osaku, A.; Kitahara, S.; Hirakawa, M.; Kariya, T. Tetrahedron Lett. 2003, 44 (40), 7521-7523. (10) Fujita, K.; Furukawa, S.; Yamaguchi, R. J. Organomet. Chem. 2002, 649 (2), 289-292. (11) Pamies, O.; Ell, A. H.; Samec, J. S. M.; Hermanns, N.; Backvall, J. E. Tetrahedron Lett. 2002, 43 (26), 4699-4702. (12) Samec, J. S. M.; Ell, A. H.; Backvall, J. E. Chem.sEur. J. 2005, 11 (8), 2327-2334. (13) Ell, A. H.; Samec, J. S. M.; Brasse, C.; Backvall, J. E. Chem. Commun. 2002 (10), 1144-1145.(14) Murahashi, S. I.; Yoshimura, N.; Tsumiyama, T.; Kojima, T. J. Am. Chem. Soc. 1983, 105 (15), 5002-5011. (15) Parvulescu, A.; De Vros, D.; Jacobs, P. Chem. Commun. 2005, (42), 5307- 5309. (16) Balkenhohl, F.; Hauer B.; Ladner, W.; Pressler, U.; Nubling, C. Resolution of the racemates of primary and secondary amines by enzyme catalysed acylation. U.S. Patent 5,728,876, 1996. (17) Rouhi, A. M. Chem. Eng. News 2004, 82 (24), 47-62. (18) Reetz, M. T.; Schimossek, K. Chimia 1996, 50 (12), 668-669. (19) Paetzold, J.; Backvall, J. E. J. Am. Chem. Soc. 2005, 127 (50), 17620- 17621. (20) Alexeeva, M.; Enright, A.; Dawson, M. J.; Mahmoudian, M.; Turner, N. J. Angew. Chem., Int. Ed. 2002, 41 (17), 3177-xxxxx. (21) Carr, R.; Alexeeva, M.; Enright, A.; Eve, T. S. C.; Dawson, M. J.; Turner, N. J. Angew. Chem., Int. Ed. 2003, 42 (39), 4807-4810. (22) Carr, R.; Alexeeva, M.; Dawson, M. J.; Gotor-Fernandez, V.; Humphrey, C. E.; Turner, N. J. ChemBioChem 2005, 6 (4), 637-639. (23) Dunsmore, C. J.; Carr, R.; Fleming, T.; Turner, N. J. A J. Am. Chem. Soc. 2006, 128 (7), 2224-2225. (24) Stirling D. I.; Z, A. L.; Matcham, G.W.; Rozzell, J. D., Jr. Enantiomeric enrichment and stereoselective synthesis of chiral amines. U.S. Patent 5,- 169,780, 1992. (25) Stirling, M. Coupled Catalytic Cycles: Development of a Procedure for the Dynamic Kinetic Resolution of Amines. Ph.D. Thesis, University of Huddersfield, Huddersfield, U.K., 2006.(26) Maitlis, P. M.; Haynes, A.; James, B. R.; Catellani, M.; Chiusoli, G. P. Dalton Trans. 2004, (21), 3409-3419. (27) Churchill, M. R.; Julis, S. A. Inorg. Chem. 1979, 18 (5), 1215-1221. (28) Kang, J. W.; Moseley, K.; Maitlis, P. M. J. Am. Chem. Soc. 1969, 91 (22), 5970-xxxx.(29) Blacker, A. J.; Campbell, L. Transfer Hydrogenation Process. WO00018708, 1998 (30) Alexeeva, M. V.; Enright, A.; Turner, N. J. Mahmoudian, M. Deracemisation of Amines. WO03080855, 2003. (31) Breen, G. F. Tetrahedron Asymm. 2004, 15 (9), 1427-1430.(32) Stirling, M.; Blacker, J.; Page, M. I. Tetrahedron Lett. 2007, 48 (7), 1247- 1250.
Depositing User: Sara Taylor
Date Deposited: 25 Jan 2008 11:52
Last Modified: 28 Aug 2021 10:38


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