Kinetic and stereochemical evidence for the involvement of only one proline molecule in the transition states of proline-catalyzed intra- and intermolecular aldol reactions

Journal of the American Chemical Society

Volumn 125, Issue 1, 2003, Pages 16-17

  Hoang, Lihn ^a   Bahmanyar, S ^b   Houk, K N ^b   List, Benjamin ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; PROLINE;

ALDOL REACTION; ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; ENANTIOSELECTIVITY; STEREOCHEMISTRY; THEORETICAL STUDY;

ALCOHOLS; ALDEHYDES; CATALYSIS; KETONES; KINETICS; PROLINE; STEREOISOMERISM;

EID: 0037425534     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja028634o     Document Type: Article

References (37)

1. (a) Hajos, Z. G.; Parrish, D. R. German Patent DE 2102623, 1971.
2. (b) Eder, U.; Sauer, G.; Wiechert, R. German Patent DE 2014757, 1971.
3. (c) Eder, U.; Sauer, G.; Wiechert, R. Angew. Chem., Int. Ed. Engl. 1971, 10, 496.
4. (d) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615.
5. (e) Hajos, Z. G. http://preprint.chemweb.com/orgchem/0209001.
6. For example Taxol: Danishefsky, S. J.; Masters, J. J.; Young, W. B.; Link, J. T.; Snyder, L. B.; Magee, T. V.; Jung, D. K.; Isaacs, R. C. A.; Bornmann, W. G.; Alaimo, C. A.; Coburn, C. A.; Di Grandi, M. J. J. Am. Chem. Soc. 1996, 118, 2843-2859.
7. (a) Gröger, H.; Wilken, J. Angew. Chem., Int. Ed. 2001, 40, 529-532.
8. (b) Jarvo, E. R.; Miller, S. J. Tetrahedron 2002. 58, 2481-2495.
9. (c) List, B. Tetrahedron 2002, 58, 5572-5590.
10. (d) List, B. Synlett 2001, 1675-1686.
11. (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396.
12. (b) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386-7387.
13. (c) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573-575.
14. For the first proline-catalyzed asymmetric intermolecular Mannich-, Michael-, and α-amination reactions, see: (d) List, B. J. Am. Chem. Soc. 2000, 122, 9336-9337.
15. (e) List, B.; Pojarliev, P.; Biller, W. T.; Martin, H. J. J. Am. Chem. Soc. 2002, 124, 827-833.
16. (f) List, B.; Pojarliev, P.; Martin, H. J. Org. Lett. 2001, 3, 2423-2425.
17. (g) List, B. J. Am. Chem. Soc. 2002, 124, 5656-5657.
18. (a) Agami, C.; Meynier, F.; Puchot, C.; Guilhem, J.; Pascard, C. Tetrahedron 1984, 40, 1031-1038.
19. (b) Agami, C.; Puchot, C.; Sevestre, H. Tetrahedron Lett. 1986, 27, 1501-1504.
20. (c) Puchot, C.; Samuel, O.; Dunach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357.
21. (d) Agami, C.; Puchot, C. J. Mol. Catal. 1986, 38, 341-343.
22. (e) Agami, C. Bull. Soc. Chim. Fr. 1987, 3, 499-507.
23. Jung, M. E. Tetrahedron 1976, 32, 3-31.
24. Brown, K. L.; Damm, L.; Dunitz, J. D.; Eschenmoser, A.; Hobi, R.; Kratky, C. Helv. Chim. Acta 1978, 61, 3108-3135.
25. (a) Bahmanyar, S.; Houk, K. N. J. Am. Chem. Soc. 2001, 123, 9922-9923.
26. (b) Bahmanyar, S.; Houk, K. N. J. Am. Chem. Soc. 2001, 123, 11273-11283.
27. (c) For quantitative stereoselectivity predictions of prolinecatalyzed intermolecular aldol reactions, see: Bahmanyar, S.; Houk, K. N., Martin, H. J., List, B. Manuscript submitted.
28. Rankin, K. N.; Gauld, J. W.; Boyd, R. J. J. Phys. Chem. A. 2002, 106, 5155-5159.
29. For related enantiogroup-differentiating aldol cyclodehydrations, see: Agami, C.; Platzer, N.; Sevestre, H. Bull. Soc. Chim. Fr. 1987, 2, 358-360.
30. (a) Sakthivel, K.; Notz, W.; Bui, T.; Barbas C. F., III. J. Am. Chem. Soc. 2001, 123, 5260-5267.
31. (b) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301-303.
32. Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798-6799.
33. Bøgevig, A.; Kumaragurubaran, N.; Jørgensen, K. A. Chem. Commun. 2002. 620-621. Also see: Bogevig, A.; Juhl, K.; Kumaragurubaran, N.; Zhuang, W.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2002, 41, 1790-1793.
34. Bøgevig, A.; Kumaragurubaran, N.; Jørgensen, K. A. Chem. Commun. 2002. 620-621. Also see: Bogevig, A.; Juhl, K.; Kumaragurubaran, N.; Zhuang, W.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2002, 41, 1790-1793.
35. Spencer, T. A.; Neel, H. S.; Fletcher, T. W.; Zayle, R. A. Tetrahedron Lett. 1965, 3889-3897.
36. One of the reviewers correctly pointed out that prevailing models for nonlinear effects do not allow for concentration dependence of ee unless the chiral entity is an auxiliary and not a catalyst. Also see: Blackmond, D. G. Acc. Chem. Res. 2000, 33, 402-411.
37. Additional detailed B3LYP/6-31G* calculations do not support a second proline molecule in the proton-transfer step (see Supporting Information). While previous calculations (ref 8) showed that intramolecular proton transfer from the proline carboxylic acid to the developing alkoxide gives a good accounting for the observed stereoselectivity, inclusion of dimethylamine as a proton-transfer mediator, produces transition states with higher activation energies and predicts that both enantiomers would be formed with nearly equal facility. Neither calculated activation energies nor stereoselectivies are consistent with a two-proline mechanism.