Direct catalytic asymmetric aldol reaction of hydroxyketones: Asymmetric Zn catalysis with a Et2Zn/linked-BINOL complex

Journal of the American Chemical Society

Volumn 125, Issue 8, 2003, Pages 2169-2178

  Kumagai, Naoya ^a   Matsunaga, Shigeki ^a   Kinoshita, Tomofumi ^a   Harada, Shinji ^a   Okada, Shigemitsu ^a   Sakamoto, Shigeru ^b   Yamaguchi, Kentaro ^b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b CHIBA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CHEMICAL REACTIONS; IONIZATION; MASS SPECTROMETRY; MOLECULAR SIEVES; NUCLEAR MAGNETIC RESONANCE; X RAY ANALYSIS; ZINC COMPOUNDS;

ALDOL REACTIONS;

KETONES;

2 HYDROXY 2' METHOXYACETOPHENONE; ACETOPHENONE DERIVATIVE; FRUCTOSE BISPHOSPHATE ALDOLASE; KETOL; UNCLASSIFIED DRUG; ZINC COMPLEX;

ALDOL REACTION; ARTICLE; CATALYSIS; CHIRALITY; DIASTEREOISOMER; ENANTIOMER; MASS SPECTROMETRY; NUCLEAR MAGNETIC RESONANCE; PHASE TRANSITION; X RAY ANALYSIS;

EID: 0037467125     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja028926p     Document Type: Article

References (76)

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3. For a general review on the catalytic enantioselective aldol reaction, see: (a) Palomo, C.; Oiarbide, M.; García, J. M. Chem.-Eur. J. 2002, 8, 37. (b) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325. (c) Nelson, S. G. Tetrahedron: Asymmetry 1998, 9, 357. (d) Gröger, H.; Vogl, E. M.; Shibasaki, M. Chem.-Eur. J. 1998, 4, 1137. (e) Carreira, E. M. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, 1999; Vol. 3, Chapter 29.1.
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12. Recent reviews for bifunctional asymmetric catalysis: (a) Shibasaki, M.; Kanai, M.; Funabashi, K. Chem. Commun. 2002, 1989. (b) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187. (c) Gröger, H. Chem.-Eur. J. 2001, 7, 5246. (d) Rowlands, G. J. Tetrahedron 2001, 57, 1865. (e) Shibasaki, M.; Kanai, M. Chem. Pharm. Bull. 2001, 49, 511. (f) Shibasaki, M. Chemtracts-Org. Chem. 1999, 12, 979. (g) Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236. (h) Sawamura, M.; Ito, Y. Chem. Rev. 1992, 92, 857.
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16. Reviews for direct catalytic asymmetric aldol reactions: (a) Alcaide, B.; Almendros, P. Eur. J. Org. Chem. 2002, 1595. (b) List, B. Tetrahedron 2002, 58, 5573. See also refs 3a, 3b, and 15b.
17. Reviews for direct catalytic asymmetric aldol reactions: (a) Alcaide, B.; Almendros, P. Eur. J. Org. Chem. 2002, 1595. (b) List, B. Tetrahedron 2002, 58, 5573. See also refs 3a, 3b, and 15b.
18. (a) Yamada, Y. M. A.; Yoshikawa, N.; Sasai, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 1871.
19. (b) Yoshikawa, N.; Yamada, Y. M. A.; Das, J.; Sasai, H.; Shibasaki. M. J. Am. Chem. Soc. 1999, 121, 4168.
20. (c) Yamada, Y. M. A.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 5561.
21. (d) Yoshikawa, N.; Shibasaki, M. Tetrahedron 2001, 57, 2569.
22. (a) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (b) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. For a partially successful attempt see: (c) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391.
23. (a) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (b) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. For a partially successful attempt see: (c) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391.
24. (a) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003. (b) Trost, B. M.; Silcoff, E. R.; Ito, H. Org. Lett. 2001, 3, 2497. For a partially successful attempt see: (c) Nakagawa, M.; Nakao, H.; Watanabe, K.-I. Chem. Lett. 1985, 391.
25. Suzuki, T.; Yamagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yamaguchi, K.; Shibasaki, M.; Noyori, R. Tetrahedron Lett. 2001, 42, 4669.
26. Mahrwald, R.; Ziemer, B. Tetrahedron Lett. 2002, 43, 4459.
27. (a) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395.
28. (b) List, B.; Pojarliev, P.; Castello, C. Org. Lett. 2001, 3, 573.
29. (c) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260. Unmodified aldehydes as donors:
30. (d) Córdova, A.; Notz, W.; Barbas, C. F., III. J. Org. Chem. 2002, 67, 301.
31. (a) Saito, S.; Nakadai, M.; Yamamoto, H. Synlett 2001, 1245. Unmodified aldehydes as donors:
32. (b) Northrup, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798.
33. (c) Bøgevig, A.; Kumaragurubaran, N.; Jørgensen, K. A. Chem. Commun. 2002, 620.
34. For impressive direct catalytic asymmetric cross-aldol reaction of unmodified aldehydes by MacMillan et al., see ref 10b. Excellent direct catalytic diastereoselective aldol reaction using chiral auxiliary was reported by Evans et al., see: (a) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392. (b) Evans, D. A.; Downey, C. W.; Shaw, J. T.; Tedrow, J. S. Org. Lett. 2002, 4, 1127.
35. For impressive direct catalytic asymmetric cross-aldol reaction of unmodified aldehydes by MacMillan et al., see ref 10b. Excellent direct catalytic diastereoselective aldol reaction using chiral auxiliary was reported by Evans et al., see: (a) Evans, D. A.; Tedrow, J. S.; Shaw, J. T.; Downey, C. W. J. Am. Chem. Soc. 2002, 124, 392. (b) Evans, D. A.; Downey, C. W.; Shaw, J. T.; Tedrow, J. S. Org. Lett. 2002, 4, 1127.
36. Review for biological and chemical methods: (a) Machajewski, T. D.; Wong, C.-H. Angew. Chem., Int. Ed. 2000, 39, 1352. For the use of catalytic antibodies, see: (b) Turner, J. M.; Bui, T.; Lerner, R. A.; Barbas, C. F., III; List, B. Chem.-Eur. J. 2000, 6, 2772 and references therein.
37. Review for biological and chemical methods: (a) Machajewski, T. D.; Wong, C.-H. Angew. Chem., Int. Ed. 2000, 39, 1352. For the use of catalytic antibodies, see: (b) Turner, J. M.; Bui, T.; Lerner, R. A.; Barbas, C. F., III; List, B. Chem.-Eur. J. 2000, 6, 2772 and references therein.
38. The use of hydroxyketones as a donor was pioneered by List et al. anti-1,2-diol: (a) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (b) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556. See also refs 9c and 13d. syn-1,2-diol: (c) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. (d) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (e) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539.
39. The use of hydroxyketones as a donor was pioneered by List et al. anti-1,2-diol: (a) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (b) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556. See also refs 9c and 13d. syn-1,2-diol: (c) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. (d) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (e) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539.
40. The use of hydroxyketones as a donor was pioneered by List et al. anti-1,2-diol: (a) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (b) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556. See also refs 9c and 13d. syn-1,2-diol: (c) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. (d) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (e) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539.
41. The use of hydroxyketones as a donor was pioneered by List et al. anti-1,2-diol: (a) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (b) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556. See also refs 9c and 13d. syn-1,2-diol: (c) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. (d) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (e) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539.
42. The use of hydroxyketones as a donor was pioneered by List et al. anti-1,2-diol: (a) Notz, W.; List, B. J. Am. Chem. Soc. 2000, 122, 7386. (b) Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002, 67, 2556. See also refs 9c and 13d. syn-1,2-diol: (c) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367. (d) Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2466. (e) Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Shibasaki, M. Org. Lett. 2001, 3, 1539.
43. 2Zn/(S,S)-linked-BINOL 1 = 2/1 complex, see refs 13d and 13e.
44. For the synthesis and application of linked-BINOL, see: (a) Matsunaga, S.; Das, J.; Roels, J.; Vogl, E. M.; Yamamoto, N.; Iida, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 2252. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Adv. Synth. Catal. 2002, 344, 4. Linked-BINOL is also commercially available from Wako Pure Chemical Industries, Ltd. Catalog No. 152-02431 for (S,S)-ligand, No. 155-02421 for (R,R)-ligand. Fax + 1-804-271-7791 (USA), +81-6-6201-5964 (Japan), +81-3-5201-6590 (Japan).
45. For the synthesis and application of linked-BINOL, see: (a) Matsunaga, S.; Das, J.; Roels, J.; Vogl, E. M.; Yamamoto, N.; Iida, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 2252. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Adv. Synth. Catal. 2002, 344, 4. Linked-BINOL is also commercially available from Wako Pure Chemical Industries, Ltd. Catalog No. 152-02431 for (S,S)-ligand, No. 155-02421 for (R,R)-ligand. Fax + 1-804-271-7791 (USA), +81-6-6201-5964 (Japan), +81-3-5201-6590 (Japan).
46. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251. (d) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. For related compounds, see: (e) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (f) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
47. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251. (d) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. For related compounds, see: (e) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (f) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
48. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251. (d) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. For related compounds, see: (e) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (f) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
49. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251. (d) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. For related compounds, see: (e) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (f) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
50. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251. (d) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. For related compounds, see: (e) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (f) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
51. For other examples of catalytic asymmetric syntheses using linked-BINOL as a chiral ligand, see: (a) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506. (b) Matsunaga, S.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2000, 41, 8473. (c) Kumagai, N.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2001, 3, 4251. (d) Takita, R.; Ohshima, T.; Shibasaki, M. Tetrahedron Lett. 2002, 43, 4661. For related compounds, see: (e) Vogl, E. M.; Matsunaga, S.; Kanai, M.; Iida, T.; Shibasaki, M. Tetrahedron Lett. 1998, 39, 7917. (f) Ishitani, H.; Kitazawa, T.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 2161 and references therein.
52. 2, gave less satisfactory results.
53. No reaction proceeded with hydroxyacetone as a donor using Zn/linked-BINOL = 2/1 complex. L-Proline afforded excellent results with hydroxyacetone. See refs 9c and 13a.
54. Utility of 2′-hydroxy-2-acetylfuran for further conversion via oxidative cleavage was demonstrated by Trost et al. Trost, B. M.; Vince, Y. S. C. Org. Lett. 2002, 4, 3513.
55. Review: Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483.
56. For selected examples of X-ray structures of bimetallic achiral zinc complexes, see: (a) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (b) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (c) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
57. For selected examples of X-ray structures of bimetallic achiral zinc complexes, see: (a) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (b) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (c) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
58. For selected examples of X-ray structures of bimetallic achiral zinc complexes, see: (a) Kaminskaia, N. V.; Spingler, B.; Lippard, S. J. J. Am. Chem. Soc. 2000, 122, 6411. (b) Koike, T.; Inoue, M.; Kimura, E.; Shiro, M. J. Am. Chem. Soc. 1996, 118, 3091. (c) Abe, K.; Izumi, J.; Ohba, M.; Yokoyama, T.; Okawa, H. Bull. Chem. Soc. Jpn. 2001, 74, 85 and references therein.
59. CIF file of crystal 9 was deposited to CCDC (CCDC 186559). See also Supporting Information.
60. The coldspray ionization mass spectrometry (CSI-MS) method enables the direct observation of labile species in solution phase: Sakamoto, S.; Fujita, M.; Kim, K.; Yamaguchi, K. Tetrahedron 2000, 56, 955 and references therein.
61. 1H NMR and CSI-MS charts mentioned in text, see Supporting Information.
62. 2Zn/1 = 2/1 solution.
63. The theoretical ion distribution pattern derived from Zn isotopes matched nicely with the observed peaks.
64. For the beneficial effects of additional achiral base to enhance the reaction rate of bifunctional asymmetric catalysis: (a) Arai, T.; Yamada, Y. M. A.; Yamamoto, N.; Sasai. H.; Shibasaki, M. Chem.-Eur. J. 1996, 2, 1368. (b) Tian, J.; Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2002, 41, 3636.
65. For the beneficial effects of additional achiral base to enhance the reaction rate of bifunctional asymmetric catalysis: (a) Arai, T.; Yamada, Y. M. A.; Yamamoto, N.; Sasai. H.; Shibasaki, M. Chem.-Eur. J. 1996, 2, 1368. (b) Tian, J.; Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2002, 41, 3636.
66. In general, it is true that the observed major species is not always an active species. However, it seems at least sure that some Zn-rich complex should be an actual active species as supported by kinetics in the following paragraph.
67. See Supporting Information for detailed results, including numerical data.
68. Judging from initial rate kinetic data alone, we cannot completely rule out the possibility that the enolization step would be the rate-determining step. Considering the drastic additive effects of MS 3A to accelerate the reaction (see section C: Second Generation System with MS 3A), we believe it more reasonable to assume that the rate-limiting step would be the product dissociation step.
69. For precedent examples where activated molecular sieves had a key role to accelerate the catalyst turn over step (the product dissociation step), see: Iida, T.; Yamamoto, N.; Sasai, H.; Shibasaki, M. J. Am. Chem. Soc. 1997, 119, 4783 and references therein.
70. For a review of catalytic enantioselective synthesis of chiral quaternary centers, see: Corey, E. J.; Guzman-Perez, A. Angew. Chem., Int. Ed. 1998, 37, 388.
71. For excellent achievements in catalytic asymmetric hydrogenation of ketones, see review: Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed. 2001, 40, 40.
72. For the construction of a chiral tert-OH group at the α-position to the carbonyl group via the diastereoselective aldol reaction using chiral auxiliary, see: (a) Kamino, T.; Murata, Y.; Kawai, N.; Hosokawa, S.; Kobayashi, S. Tetrahedron Lett. 2001, 42, 5249. For the construction of a chiral tert-OH group at the β-position to the carbonyl group via kinetic resolution (enantioselective retroaldol reaction) using catalytic antibody, see: (b) List, B.; Shabat, D.; Zhong, G.; Turner, J. M.: Li, A.; Bui, T.: Anderson, J.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 1999, 121, 7283.
73. For the construction of a chiral tert-OH group at the α-position to the carbonyl group via the diastereoselective aldol reaction using chiral auxiliary, see: (a) Kamino, T.; Murata, Y.; Kawai, N.; Hosokawa, S.; Kobayashi, S. Tetrahedron Lett. 2001, 42, 5249. For the construction of a chiral tert-OH group at the β-position to the carbonyl group via kinetic resolution (enantioselective retroaldol reaction) using catalytic antibody, see: (b) List, B.; Shabat, D.; Zhong, G.; Turner, J. M.: Li, A.; Bui, T.: Anderson, J.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 1999, 121, 7283.
74. Tamura, Y.; Fujiwara, H.; Sumoto, K.; Ikeda, M.: Kita, Y. Synthesis 1973, 215.
75. (a) Porter, J. R.; Traverse, J. F.; Hoveyda, A. H.; Snapper, M. C. J. Am. Chem. Soc. 2001, 123, 10409.
76. (b) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180 and references therein.