Polystyrene-supported (R)-2-piperazino-1,1,2-triphenylethanol: A readily available supported ligand with unparalleled catalytic activity and enantioselectivity

Journal of Organic Chemistry

Volumn 70, Issue 2, 2005, Pages 433-438

  Castellnou, David ^a   Solà, Lluís ^b   Jimeno, Ciril ^b   Fraile, José M ^c   Mayoral, José A ^c   Riera, Antoni ^a   Pericàs, Miquel A ^a,b  

^a INSTITUTE OF CHEMICAL RESEARCH OF CATALONIA ICIQ   (Spain)

^b UNIVERSITY OF BARCELONA   (Spain)

^c UNIVERSITY OF ZARAGOZA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; CATALYST ACTIVITY; MATRIX ALGEBRA; PERTURBATION TECHNIQUES; RESINS;

CATALYTIC RESINS; ETHYLATION; POLYMER MATRIX;

POLYSTYRENES;

2 (4 BENZYLPIPERAZIN 1 YL) 1,1,2 TRIPHENYLETHANOL; LIGAND; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CHEMICAL STRUCTURE; CONTROLLED STUDY; ENANTIOSELECTIVITY; PROTON NUCLEAR MAGNETIC RESONANCE; RING OPENING;

EID: 12344316678     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo048310d     Document Type: Article

References (24)

1. Oldest hit in SciFinder for green chemistry: Pavel, D. Chem. Listy 1991, 85, 1144-1149.
2. (a) Bräse, S.; Lauterwasser, F.; Ziegert, R. E. Adv. Synth. Catal. 2003, 345, 862-929.
3. (b) Special Issue on Recoverable Catalysts and Reagents; Gladisz, J. A., Ed. Chem. Rev. 2002, 102, 3215-3892.
4. (c) Chiral Catalyst Immobilization and Recycling; de Vos, D. E., Vankelekom, I. F. J., Jacobs, P. A., Eds.; Wiley-VCH: Weinheim, Germany, 2000.
5. For a successful, polymer-supported yet soluble ligand for enantioselective phenylation of aldehydes, see: Bolm, C.; Hermanns, N.; Classen, A.; Muñiz, K. Bioorg. Med. Chem. Lett. 2002, 12, 1795-1798.
6. (a) Itsuno, S.; Fréchet, J. M. J. J. Org. Chem. 1987, 52, 4140-4142.
7. (b) Soai, K.; Niwa, S.; Watanabe, M. J. Org. Chem. 1988, 53, 927-928.
8. For 3, see: ten Holte, P.; Wijgergangs, J.-P.; Thijs, L.; Zwannenburg, B. Org. Lett. 1999, 1, 1095-1097. For 4, see: Burguete, M. I.; Garcia-Verdugo, E.; Vicent, M. J.; Luis, S. V.; Pennemann, H.; Graf von Keyserling, N.; Martens, J. Org. Lett. 2002, 4, 3947-3950.
9. For 3, see: ten Holte, P.; Wijgergangs, J.-P.; Thijs, L.; Zwannenburg, B. Org. Lett. 1999, 1, 1095-1097. For 4, see: Burguete, M. I.; Garcia-Verdugo, E.; Vicent, M. J.; Luis, S. V.; Pennemann, H.; Graf von Keyserling, N.; Martens, J. Org. Lett. 2002, 4, 3947-3950.
10. (a) For insoluble, polymer-supported amino alcohol ligands whose anchoring does not involve the amino moiety, see: Vidal-Ferran, A.; Bampos, N.; Moyano, A.; Pericàs, M. A.; Riera, A.; Sanders, J. K. M. J. Org. Chem. 1998, 63, 6309-6318.
11. (b) For soluble, polymer-supported ligands with positive support effects, see: Fan, Q.-H.; Wang, R.; Chan, A. S. C. Bioorg. Med. Chem. Lett. 2002, 12, 1867-1871 and references therein.
12. (a) Solà, L.; Reddy, K. S.; Vidal-ferran, A.; Moyano, A.; Pericàs, M. A.; Riera, A.; Alvarez-Larena, A.; Piniella, J.-F. J. Org. Chem. 1998, 63, 7078-7082.
13. (b) Fontes, M.; Verdaguer, X.; Solà, L.; Pericàs, M. A.; Riera, A. J. Org. Chem. 2004, 69, 2532-2543.
14. (c) García-Delgado, N.; Fontes, M.; Pericàs, M. A.; Riera, A.; Verdaguer, X. Tetrahedron: Asymmetry 2004, 15, 2085-2090.
15. Pericàs, M. A.; Castellnou, D.; Rodríguez, I.; Riera, A.; Solà, L. Adv. Synth. Catal. 2003, 345, 1305-1313.
16. Chini, M.; Crotti, P.; Flippin, L. A.; Gardelli, C.; Giovani, E.; Macchia, F.; Pineschi, M. J. Org. Chem. 1993, 58, 1221-1227.
17. This epoxide can be routinely prepared at the molar scale in >99.9% ee by Jacobsen epoxidation of triphenylethylene (Brandes, B. D.; Jacobsen, E. N. J. Org. Chem. 1994, 59, 4378-4380) and recrystallization from hexane.
18. max [mmol ligand/g resin], the maximum ligand substitution level, is calculated as described in ref 6.
19. For the immobilization of 8 on silica by sol-gel synthesis and grafting, see: Fraile, J. M.; Mayoral, J. A.; Serrano, J.; Pericàs, M. A.; Solà, L.; Castellnou, D. Org. Lett. 2003, 5, 4333-4335.
20. At -10°C, all substrates reacted completely in 24 h. At -20 °C, over 90% conversion was recorded for all substrates in 24 h.
21. In the context of this research, most practical conditions are those involving the minimal catalyst amount leading to complete conversion at the nearest to ambient temperature in the shortest reaction time with an affordable decrease in enantioselectivity with respect to its optimal value.
22. For a discussion on the conversion of heat flow data into kinetic data see, for instance: Nielsen, L. P. C.; Stevenson, C. P.; Blackmond, D. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 1360-1362, and the Supporting Information.
23. Kitamura, M.; Suga, S.; Kawai, K.; Noyori, R. J. Am. Chem. Soc. 1986, 108, 6071-6072.
24. For the five examples where direct comparison is possible (10e, 10j, 10k, 10l, 10m) the mean enantiomeric excess recorded with (-)-DAIB (2 mol %) is 87.6%, and that recorded with 7 (2 mol %) is 88.4%.