Dynamic processes in the copper-catalyzed substitution of chiral allylic acetates lending to loss of chiral information

Chemistry - A European Journal

Volumn 13, Issue 14, 2007, Pages 4094-4102

  Norinder, Jakob ^a   Bäckvall, Jan E ^a  

^a STOCKHOLM UNIVERSITY   (Sweden)

Author keywords

Allylic substitution; Chirality; Copper; Dynamic processes; Heterogeneous catalysis; Racemization

Indexed keywords

CATALYSIS; CHIRALITY; COPPER; REACTION KINETICS; STEREOCHEMISTRY; SUBSTITUTION REACTIONS;

ALLYLIC SUBSTITUTION; DYNAMIC PROCESSES; GRIGNARD REAGENTS; RACEMIZATION;

ESTERS;

ACETIC ACID DERIVATIVE; COPPER; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; SOLVENT;

ARTICLE; CATALYSIS; CHEMISTRY; KINETICS; OXIDATION REDUCTION REACTION; STEREOISOMERISM; TEMPERATURE;

ACETATES; CATALYSIS; COPPER; INDICATORS AND REAGENTS; KINETICS; OXIDATION-REDUCTION; SOLVENTS; STEREOISOMERISM; TEMPERATURE;

EID: 34250308301     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200601684     Document Type: Article

References (47)

1. a) J. Halpern, B. M. Trost, Proc. Natl. Acad. Sci. USA 2004, 101, 5347;
2. b) Catalytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Ojima), Wiley-VCH, Weinheim , 2000;
3. c) Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto). Springer. Berlin. 1999;
4. d) R. Noyori in Asymmetric Catalysis in Organic Synthesis, Wiley, New York, 1994;
5. c) O. Pàmies, J. E. Bäckvall, Chem. Rev. 2003, 103, 3247;
6. f) K. Faber, Biotransformations in Organic Chemistry. 5th ed, Springer: Berlin. 2004;
7. g) P. I. Dalko, L. Moisan, Angew. Chem. 2004, 116, 5248;
8. Angew. Chem. Int. Ed. 2004, 43, 5138.
9. a) B. L. Feringa, R. Naasz, R. Imbos, A. L. Arnold, In Modern Organocopper Chemistry, (Ed.: N. Krause), Wiley-VCH, Weinhem (Germany). 2002, p. 224;
10. b) S. Woodward, Angew. Chem. 2005, 117, 5696;
11. Angew. Chem. Int. Ed. 2005, 44, 5560;
12. c) A. Alexakis, C. Benheim, Eur. J. Org. Chem. 2002, 3221;
13. d) N. Krause, A. Hoffmann Röder, Synthesis 2001, 171.
14. a) A. S. E. Karlström, J.-E. Bäckvall, In Modern Organocopper Chemistry (Ed.: N. Krause). Wiley-VCH, Weinhem (Germany), 2002, p. 259;
15. b) A. Alexakis, C. Malan, L. Lea, K. Tissot-Croset, D. Polet, C. Falciola, Chimia. 2006, 60, 124;
16. c) H. Yorimitsu, K. Oshima, Angew. Chem. 2006, 118, 4509;
17. Angew. Chem. Int. Ed. 2006, 45, 4435.
18. For some recent selected references on Cu-catalyzed enantioselective 1.4-additions and γ-substitution of allylic electrophiles see: a) F. López, S. R. Harutyunyan, A. Meetsma, A. J. Minnaard, B. L. Feringa, Angew. Chem. 2005, 117, 2812;
19. Angew. Chem. Int. Ed. 2005, 44, 2752;
20. b) J. J. Van Veldhuizen, J. E. Campbell, R. E. Giudici, A. H. Hoveyda, J. Am. Chem. Soc. 2005, 127, 6877;
21. c) C. A. Falciola, K. Tissot-Croset. A. Alexakis, Angew. Chem. 2006, 118, 6141;
22. Angew. Chem. Int. Ed. 2006, 45, 5995.
23. For related studies on palladium-catalyzed substitution reactions of allylic substrates see: a) P. R. Auburn, P. B. Mackenzie, B. Bosnien, J. Am. Chem. Soc. 1985, 107, 2033;
24. b) P. B. Mackenzie, J. Whelan, B. Bosnich, J. Am. Chem. Soc. 1985, 107, 2046;
25. c) B. M. Trost, R. C. Bunt, R. C. Lemoine, T. L. Calkins, J. Am. Chem. Soc. 2000, 122, 5968;
26. d) B. M. Trost, Chem. Pharm. Bull. 2002, 50, 1.
27. a) J. I. Seeman, Chem. Rev. 1983, 83, 83;
28. b) R. E. Gawley, J. Aubé, J. Baldwin, Principles of Asymmetric Synthesis (Eds.: J. E. Baldwin, P. D. Magnus), Elsevier Science, 1995.
29. 5.
30. a) E. S. M. Persson, J.-E. Bäckvall, Acta Chem. Scand. 1995, 49, 899;
31. b) J.-E. Bäckvall, M. Sellén, B. Grant, J. Am. Chem. Soc. 1990, 112, 6615;
32. c) J.-E. Bäckvall, M. Sellén, J. Chem. Soc. Chem. Commun. 1987, 827;
33. d) A. S. E. Karlström, J. E. Bäckvall, Chem. Eur. J. 2001, 7, 1981-1989.
34. Attempts to use more sterically hindered alkyl Grignard reagents such as cyclohexylmagnesium bromide or isopropylmagnesium bromide gave complex product mixtures.
35. L. H. Goering. S. S. Kantner, E. P. Seitz. J. Org. Chem. 1985, 50, 5495.
36. Optical rotation of this product was close to zero. In the absence of a reference value, the product was considered practically racemic.
37. III complexes. M. Yamanaka, S. Kato, E. Nakamura. J. Am. Chem. Soc. 2004, 126, 6287.
38. J. Norinder, J.-E. Bäckvall, N. Yoshikai, E. Nakamura, Organometallies 2006, 25, 2129.
39. P. H. J. Carlsen, T. Katsuki, V. S. Martin, K. B. Sharpless. J. Org. Chem. 1981, 46, 3936.
40. a) M. Cygler, P. Grochulski, R. J. Kazlauskas, J. D. Schrag, F. Bouthillier, B. Rubin, A. N. Serriqi, A. K. Gupta, J. Am. Chem. Soc. 1994, 116, 3180;
41. b) R. J. Kazlauskas, A. N. E. Weissfloch, A. T. Rappaport, L. A. Cuccia. J. Org. Chem. 1991, 56, 2656.
42. P. Bharathi, M. Periasami, Org. Lett. 1999, 1, 857.
43. M. Nyerges, A. Arany, I. Fejes, P. W. Groundwater, W. Zhang, D. BeBcndellndell, R. J. Anderson, L. Tõke, Tetrahedron 2002, 58, 989.
44. G. J. Dawson, J. M. J. Williams, Tetrahedron; Asymmetry 1995, 6, 2535.
45. J. L. Stavinoha, P. S. Mariano, A. Leone-Bay, R. Swanson, C. Bracken. J. Am. Chem. Soc. 1981, 103, 3148.
46. J. Norinder, K. Bogár, L. Kanupp, J.-E. Bäckvall, unpublished results.
47. J. L. Belelie, J. M. Chong, J. Org. Chem. 2001, 66, 5552.