Physical and chemical rationalization for asymmetric amplification in aatocatalytic reactions

Angewandte Chemie - International Edition

Volumn 43, Issue 16, 2004, Pages 2099-2103

  Buono, Frederic G ^a   Iwamura, Hiroshi ^a   Blackmond, Donna G ^a  

^a IMPERIAL COLLEGE LONDON   (United Kingdom)

Author keywords

Asymmetric amplification; Asymmetric catalysis; Autocatalysis; Chirality; Kinetics

Indexed keywords

AMPLIFICATION; CHEMICAL REACTIONS; SOLUTIONS; SOLVENTS; SUBSTRATES;

CHIRALS; ENANTIOMERS; SYNERGISTIC EFFECTS;

CATALYSTS;

ALDEHYDE; PYRIMIDINE; SOLVENT;

ALKYLATION; ARTICLE; ASYMMETRIC CATALYSIS; CATALYST; CHIRALITY; CITRIC ACID CYCLE; ENANTIOMER; MICROENVIRONMENT; MOLECULAR DYNAMICS; MOLECULAR INTERACTION; MOLECULAR MECHANICS; POLYMERIZATION; QUANTUM CHEMISTRY; REACTION ANALYSIS; SOLVATION; STRUCTURE ANALYSIS;

EID: 4544284243     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200353086     Document Type: Article

References (27)

1. M. Calvin, Chemical Evolution, Oxford University Press, Oxford, 1969.
2. D. K. Kondepudi, Science 1990, 250, 975.
3. F. C. Frank, Biochim. Biophys Acta 1953, 11, 459.
4. For recent reviews on spontaneous asymmetric synthesis, see: a) K. Mislow, Collect. Czech. Chem. Commun. 2003, 68, 849;
5. b) B. L. Feringa, R. A. van Delden, Angew. Chem. 1999, 111, 3624; Angew. Chem. Int. Ed. 1999, 38, 3418;
6. b) B. L. Feringa, R. A. van Delden, Angew. Chem. 1999, 111, 3624; Angew. Chem. Int. Ed. 1999, 38, 3418;
7. c) H. Buschmann, R. Thede, D. Heller, Angew. Chem. 2000, 112, 4197; Angew. Chem. Int. Ed. 2000, 39, 4033;
8. c) H. Buschmann, R. Thede, D. Heller, Angew. Chem. 2000, 112, 4197; Angew. Chem. Int. Ed. 2000, 39, 4033;
9. d) D. K. Kondepudi, K. Asakura, Acc. Chem. Res. 2001, 34, 946;
10. e) M. Avalos, R. Babiano, P. Cintas, J. L. Jimenez, J. C. Palacios, Chem. Commun. 2000, 887, and references therein.
11. First publications: a) K. Soai, T. Shibata, H. Morioka, K. Choji, Nature 1995, 378, 767;
12. b) T. Shibata, K. Choji, T. Hayase, Y. Aizu, K. Soai, Chem. Commun. 1996, 1235;
13. c) T. Shibata, H. Morioka, T. Hayase, K. Choji, K. Soai, J. Am. Chem. Soc. 1996, 118, 471; for a recent review, see: K. Soai, I. Sato, Chirality 2002, 14, 548.
14. c) T. Shibata, H. Morioka, T. Hayase, K. Choji, K. Soai, J. Am. Chem. Soc. 1996, 118, 471; for a recent review, see: K. Soai, I. Sato, Chirality 2002, 14, 548.
15. a) D. G. Blackmond, C. R. McMillan, S. Ramdeehul, A. Schorm, J. M. Brown. J. Am. Chem. Soc. 2001, 123, 10103;
16. b) D. G. Blackmond, Adv. Synth. Catal. 2002, 344, 156;
17. c) F. G. Buono, D. G. Blackmond, J. Am. Chem. Soc. 2003, 125, 8978.
18. a) C. Puchot, O. Samuel, E. Duñach, S. Zhao, C. Agami, H. B. Kagan, J. Am. Chem. Soc. 1986, 108, 2353;
19. b) D. Guillaneux, S. H. Zhao, O. Samuel, D. Rainford, H. B. Kagan, J. Am. Chem. Soc. 1994, 116, 9430.
20. Reactions in toluene, diethyl ether, and toluene/diethyl ether mixtures show complete conversion of aldehyde 1 into the alkylation product 2 upon workup. Reactions in THF show significant side reactions, including reduction to the primary pyrimidyl alcohol.
21. K. Soai, L. Sato, T. Shibata, S. Komiya, M. Hayashi, Y. Matsueda, H. Imamura, T. Hayase, H. Morioka, H. Tabira, J. Yamamoto, Y. Kowata, Tetrahedron: Asymmetry 2003, 14, 185.
22. prod
23. C. Bolm, G. Schlinghoff, K. Harms, Chem. Ber. 1992, 125, 1191.
24. D. A. Singleton, L. K. Vo, J. Am. Chem. Soc. 2002, 124, 10010.
25. The similarity in the rate profiles and asymmetric amplification observed for reactions carried out under similar conditions in diethyl ether, toluene, and toluene/diethyl ether mixtures, and their compliance with the model proposed in reference [6c], suggest that the reactive intermediate itself may be similar in different solvents.
26. I. D. Gridnev, J. M. Serafimov, H. Quiney, J. M. Brown, Org. Biomol. Chem. in press.
27. J. S. Siegel, Nature 2002, 419, 346.