From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction

Angewandte Chemie - International Edition

Volumn 55, Issue 30, 2016, Pages 8691-8695

  Ríos Lombardía, Nicolás ^a   Vidal, Cristian ^b   Liardo, Elisa ^a   Morís, Francisco ^a   García Álvarez, Joaquín ^b   González Sabín, Javier ^a  

^a Campus El Cristo   (Spain)

^b UNIVERSITY OF OVIEDO   (Spain)

Author keywords

alcohols; chirality; enzyme catalysis; isomerization; transition metals

Indexed keywords

ALCOHOLS; BIOCATALYSTS; CATALYSIS; CHIRALITY; ENANTIOSELECTIVITY; ISOMERS; KETONES; RUTHENIUM; TRANSITION METALS;

ASYMMETRIC BIOREDUCTION; ASYMMETRIC REDUCTION; CASCADE REACTIONS; CONCURRENT PROCESS; ENZYME CATALYSIS; MILD REACTION CONDITIONS; MULTI-STEP APPROACHES; REDOX ISOMERIZATION;

ISOMERIZATION;

EID: 84973364522     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201601840     Document Type: Article

References (49)

1. P. T. Anastas, J. C. Warner, Green Chemistry Theory and Practice, Oxford University Press, Oxford, 1998.
2. U. M. Lindström, Organic Reactions in Water: Principles, Strategies and Applications, Blackwell Publishing, Oxford, 2007;
3. M.-O. Simon, C.-J. Li, Chem. Soc. Rev. 2012, 41, 1415.
4. S. F. Mayer, W. Kroutil, K. Faber, Chem. Soc. Rev. 2001, 30, 332;
5. A. Bruggink, R. Schoevaart, T. Kieboom, Org. Process Res. Dev. 2003, 7, 622;
6. J. M. Lee, Y. Na, H. Han, S. Chang, Chem. Soc. Rev. 2004, 33, 302;
7. Y. Hayashi, Chem. Sci. 2016, 7, 866.
8. For combinations of metal catalyst and organocatalyst, see: A. Quintard, A. Alexakis, C. Mazet, Angew. Chem. Int. Ed. 2011, 50, 2354;
9. Angew. Chem. 2011, 123, 2402; for a combination of an organocatalyst with an enzyme, see:
10. K. Baer, M. Krauβer, E. Burda, W. Hummel, A. Berkessel, H. Gröger, Angew. Chem. Int. Ed. 2009, 48, 9355;
11. Angew. Chem. 2009, 121, 9519.
12. A. Cuetos, F. R. Bisogno, I. Lavandera, V. Gotor, Chem. Commun. 2013, 49, 2625.
13. H. Sato, W. Hummel, H. Gröger, Angew. Chem. Int. Ed. 2015, 54, 4488;
14. Angew. Chem. 2015, 127, 4570.
15. E. Burda, W. Hummel, H. Gröger, Angew. Chem. Int. Ed. 2008, 47, 9551;
16. Angew. Chem. 2008, 120, 9693;
17. A. Boffi, S. Cacchi, P. Ceci, R. Cirilli, G. Fabrizi, A. Prastaro, S. Niembro, A. Shafir, A. Vallribera, ChemCatChem 2011, 3, 347.
18. K. Tenbrink, M. Sebler, J. Schatz, H. Gröger, Adv. Synth. Catal. 2011, 353, 2363;
19. C. A. Denard, H. Huang, M. J. Bartlett, L. Lu, Y. Tan, H. Zhao, J. F. Hartwig, Angew. Chem. Int. Ed. 2014, 53, 465;
20. Angew. Chem. 2014, 126, 475.
21. The only exception would be the dynamic kinetic resolutions (DKRs) combining a racemizing metal catalyst with a biotransformation, although almost exclusively in organic solvent:
22. S. Agrawal, E. Martínez-Castro, R. Marcos, B. Martín-Matute, Org. Lett. 2014, 16, 2256;
23. O. Verho, J.-E. Bäckvall, J. Am. Chem. Soc. 2015, 137, 3996. Additionally, Kroutil and co-workers combined an iridium-catalyzed oxidation with a bioreduction in aqueous medium, but it led to disappointing enantioselectivities:
24. F. G. Mutti, A. Orthaber, J. H. Schrittwieser, J. G. de Vries, R. Pietschnig, W. Kroutil, Chem. Commun. 2010, 46, 8046.
25. N. Ríos-Lombardía, C. Vidal, M. Cocina, F. Morís, J. García-Álvarez, J. González-Sabín, Chem. Commun. 2015, 51, 10937.
26. Asymmetric reduction of allylic alcohols has proven to be a challenging process: H. Matsuda, S. Ando, T. Morikawa, S. Kataoka, M. Yoshikawa, Bioorg. Med. Chem. Lett. 2005, 15, 1949.
27. The ruthenium-catalyzed isomerization/asymmetric transfer hydrogenation of allylic alcohols in dry organic solvents and using high temperatures has been reported:
28. R. Wu, M. G. Beauchamps, J. M. Laquidara, J. R. Sowa, Jr., Angew. Chem. Int. Ed. 2012, 51, 2106;
29. Angew. Chem. 2012, 124, 2148;
30. T. Slagbrand, H. Lundberg, H. Adolfsson, Chem. Eur. J. 2014, 20, 16102.
31. For a related nonchiral chemoenzymatic process, see: Z. J. Wang, K. N. Clary, R. G. Bergman, K. N. Raymond, F. D. Toste, Nat. Chem. 2013, 5, 100.
32. S. Gargiulo, D. J. Opperman, U. Hanefeld, I. W. C. E. Arends, F. Hollmann, Chem. Commun. 2012, 48, 6630.
33. T. Knaus, C. E. Paul, C. W. Levy, S. De Vries, F. G. Mutti, F. Hollmann, N. S. Scrutton, J. Am. Chem. Soc. 2016, 138, 1033.
34. J. García-Álvarez, J. Gimeno, F. J. Suárez, Organometallics 2011, 30, 2893. For recent examples of redox isomerization/hydrogenation or halogenation of allylic alcohols, see:
35. L. Mantilli, D. Gérard, S. Torche, C. Besnard, C. Mazet, Angew. Chem. Int. Ed. 2009, 48, 5143;
36. Angew. Chem. 2009, 121, 5245;
37. N. Ahlsten, A. Bermejo Gómez, B. Martín-Matute, Angew. Chem. Int. Ed. 2013, 52, 6273;
38. Angew. Chem. 2013, 125, 6393;
39. A. Bermejo Gómez, E. Erbing, M. Batuecas, A. Vázquez-Romero, B. Martín-Matute, Chem. Eur. J. 2014, 20, 10703.
40. V. Cadierno, P. Crochet, J. Francos, S. E. García-Garrido, J. Gimeno, N. Nebra, Green Chem. 2009, 11, 1992;
41. A. E. Díaz-Álvarez, P. Crochet, V. Cadierno, Catal. Commun. 2011, 13, 91;
42. V. Bizet, X. Pannecoucke, J.-L. Renaud, D. Caharda, Adv. Synth. Catal. 2013, 355, 1394.
43. A parametric study of the catalytic activity of complexes 1–3 with 4 a under different catalytic conditions is shown in Table S1 in the ESI.
44. KRED Screening KitThe Codex® (Codexis) contains 24 ketoreductases. For the full panel of enzymatic results, see the Supporting Information.
45. W. Stampfer, B. Kosjek, K. Faber, W. Kroutil, J. Org. Chem. 2003, 68, 402;
46. J. A. Johnson, W. S. Akers, V. L. Herring, M. S. Wolf, J. M. Sullivan, Pharmacotherapy 2000, 20, 622.
47. This fact reveals inhibition by KREDs and NADPH towards 2, and is in contrast to the previous experiments (Table S1, entries 6 and 7).
48. N. K. Modukuru, J. Sukumaran, S. J. Collier, A. S. Chan, A. Gohel, G. W. Huisman, R. Keledjian, K. Narayanaswamy, S. J. Novick, S. M. Palanivel, D. Smith, Z. Wei, B. Wong, W. L. Yeo, D. A. Entwistle, Org. Process Res. Dev. 2014, 18, 810.
49. Three different batches of KRED-P1-A04, were tested and the results were within the 80–85 % range for the saturated alcohol 4 c.