Chiral amine-catalyzed asymmetric Baylis-Hillman reaction: A reliable route to highly enantiomerically enriched (α-methylene-β-hydroxy)esters [5]

Journal of the American Chemical Society

Volumn 121, Issue 43, 1999, Pages 10219-10220

  Iwabuchi, Yoshiharu ^a   Nakatani, Mari ^a   Yokoyama, Nobiko ^a   Hatakeyama, Susumi ^a  

^a NAGASAKI UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACRYLIC ACID DERIVATIVE; ALDEHYDE DERIVATIVE; AMINE; BENZALDEHYDE DERIVATIVE; ESTER DERIVATIVE; METHYL GROUP; N,N DIMETHYLFORMAMIDE; NITRO DERIVATIVE; QUINIDINE DERIVATIVE;

CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRAL CHROMATOGRAPHY; CHIRALITY; CONTROLLED STUDY; ENANTIOMER; LETTER; STEREOCHEMISTRY;

EID: 0033520752     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992655+     Document Type: Letter

References (29)

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3. For leading references, see: (a) Markó, I. E. Organometallic Reagents in Organic Synthesis; Academic Press: London, 1994. (b) Piber, M.; Leahy, J. W. Tetrahedron Lett. 1998, 39, 2043-2046. (c) Familoni, O. B.; Kaye, P. T.; Klaas, P. J. J. Chem. Soc., Chem. Commun. 1998, 2563-2564.
4. For leading references, see: (a) Markó, I. E. Organometallic Reagents in Organic Synthesis; Academic Press: London, 1994. (b) Piber, M.; Leahy, J. W. Tetrahedron Lett. 1998, 39, 2043-2046. (c) Familoni, O. B.; Kaye, P. T.; Klaas, P. J. J. Chem. Soc., Chem. Commun. 1998, 2563-2564.
5. For mechanistic studies, see: (a) Hoffmann, H. M. R.; Rabe, J. Angew. Chem. 1983, 95, 795-796. (b) Hill, J. S.; Isaacs, N. S. J. Phys. Org. Chem. 1990, 3, 285-293. (c) Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. (d) Fort, Y.; Berthe, M. C.; Caubere, P. Tetrahedron 1992, 48, 6371-6384. (e) Rosendaal, E. M. L.; Voss, B. M. W.; Scheeren, H. W. Tetrahedron 1993, 31, 6931-6936.
6. For mechanistic studies, see: (a) Hoffmann, H. M. R.; Rabe, J. Angew. Chem. 1983, 95, 795-796. (b) Hill, J. S.; Isaacs, N. S. J. Phys. Org. Chem. 1990, 3, 285-293. (c) Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. (d) Fort, Y.; Berthe, M. C.; Caubere, P. Tetrahedron 1992, 48, 6371-6384. (e) Rosendaal, E. M. L.; Voss, B. M. W.; Scheeren, H. W. Tetrahedron 1993, 31, 6931-6936.
7. For mechanistic studies, see: (a) Hoffmann, H. M. R.; Rabe, J. Angew. Chem. 1983, 95, 795-796. (b) Hill, J. S.; Isaacs, N. S. J. Phys. Org. Chem. 1990, 3, 285-293. (c) Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. (d) Fort, Y.; Berthe, M. C.; Caubere, P. Tetrahedron 1992, 48, 6371-6384. (e) Rosendaal, E. M. L.; Voss, B. M. W.; Scheeren, H. W. Tetrahedron 1993, 31, 6931-6936.
8. For mechanistic studies, see: (a) Hoffmann, H. M. R.; Rabe, J. Angew. Chem. 1983, 95, 795-796. (b) Hill, J. S.; Isaacs, N. S. J. Phys. Org. Chem. 1990, 3, 285-293. (c) Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. (d) Fort, Y.; Berthe, M. C.; Caubere, P. Tetrahedron 1992, 48, 6371-6384. (e) Rosendaal, E. M. L.; Voss, B. M. W.; Scheeren, H. W. Tetrahedron 1993, 31, 6931-6936.
9. For mechanistic studies, see: (a) Hoffmann, H. M. R.; Rabe, J. Angew. Chem. 1983, 95, 795-796. (b) Hill, J. S.; Isaacs, N. S. J. Phys. Org. Chem. 1990, 3, 285-293. (c) Bode, M. L.; Kaye, P. T. Tetrahedron Lett. 1991, 32, 5611-5614. (d) Fort, Y.; Berthe, M. C.; Caubere, P. Tetrahedron 1992, 48, 6371-6384. (e) Rosendaal, E. M. L.; Voss, B. M. W.; Scheeren, H. W. Tetrahedron 1993, 31, 6931-6936.
10. (a) Markó, I. E.; Giles, P. R.; Hindley, N. J. Tetrahedron 1997, 53, 1015-1024.
11. (b) Hayase, T.; Shibata, T.; Soai, K.; Wakatsuki, Y. J. Chem. Soc., Chem. Commun. 1998, 1271-1272.
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13. (d) Kataoka, T.; Iwama, T.; Tsujiyama, S.; Kanematsu, K.; Iwamura, T.; Watanabe, S. Chem. Lett. 1999, 257-258. See also ref 1.
14. Brzezinski, L. J.; Rafel, S.; Leahy, J. W. J. Am. Chem. Soc. 1997, 119, 4317-4318.
15. The Baylis-Hillman reaction is notorious for slow reaction rates, and a number of attempts have been made to circumvent the sluggish nature of this reaction. (a) Drewes, S. E.; Freese, S. D.; Emslie, N. D.; Roos, G. H. P. Synth. Commun. 1988, 18, 1565. (b) Rafel, S.; Leahy, J. W. J. Org. Chem. 1997, 62, 1521-1522. (c) Kawamura, M.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 1539-1542. See also ref 1.
16. The Baylis-Hillman reaction is notorious for slow reaction rates, and a number of attempts have been made to circumvent the sluggish nature of this reaction. (a) Drewes, S. E.; Freese, S. D.; Emslie, N. D.; Roos, G. H. P. Synth. Commun. 1988, 18, 1565. (b) Rafel, S.; Leahy, J. W. J. Org. Chem. 1997, 62, 1521-1522. (c) Kawamura, M.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 1539-1542. See also ref 1.
17. The Baylis-Hillman reaction is notorious for slow reaction rates, and a number of attempts have been made to circumvent the sluggish nature of this reaction. (a) Drewes, S. E.; Freese, S. D.; Emslie, N. D.; Roos, G. H. P. Synth. Commun. 1988, 18, 1565. (b) Rafel, S.; Leahy, J. W. J. Org. Chem. 1997, 62, 1521-1522. (c) Kawamura, M.; Kobayashi, S. Tetrahedron Lett. 1999, 40, 1539-1542. See also ref 1.
18. Bailey, M.; Markó, I. E.; Ollis, D.; Rasmussen, P. R. Tetrahedron Lett. 1990, 31, 4509-4512.
19. 9 (15%), whereas the reaction of 1a with methyl acrylate (3) took 12 days to achieve 94% conversion.
20. The dioxanones are often produced in the reactions using the reactive acrylates. (a) Drewes, S. E.; Emslie N. D.; Karodia, N.; Khan, A. A. Chem. Ber. 1990, 123, 1447. (b) Perlmutter, P.; Puniani, E.; Westman, G. Tetrahedron Lett. 1996, 37, 1715. See also ref 5.
21. The dioxanones are often produced in the reactions using the reactive acrylates. (a) Drewes, S. E.; Emslie N. D.; Karodia, N.; Khan, A. A. Chem. Ber. 1990, 123, 1447. (b) Perlmutter, P.; Puniani, E.; Westman, G. Tetrahedron Lett. 1996, 37, 1715. See also ref 5.
22. The catalysts QD-1-QD-4 were prepared according to the literature procedures. (a) von Riesen, C.; Hoffmann, H. M. R. Chem. Eur. J. 1996, 2, 680-684. (b) Braje, W.; Frackenpohl, J.; Langer, P.; Hoffmann, H. M. R. Tetrahedron 1998, 54, 3495-3512. We found that a multigram sample of QD-4 was synthesized (∼60%) in one step from (+)-quinidine by heating with 10 equiv of KBr in 85% phosphoric acid at 100°C for 5 days.
23. The catalysts QD-1-QD-4 were prepared according to the literature procedures. (a) von Riesen, C.; Hoffmann, H. M. R. Chem. Eur. J. 1996, 2, 680-684. (b) Braje, W.; Frackenpohl, J.; Langer, P.; Hoffmann, H. M. R. Tetrahedron 1998, 54, 3495-3512. We found that a multigram sample of QD-4 was synthesized (∼60%) in one step from (+)-quinidine by heating with 10 equiv of KBr in 85% phosphoric acid at 100°C for 5 days.
24. Solvent effects could not be evaluated due to the low solubility of the catalysts in solvents other than DMF.
25. This supposition is well supported by their stereostruclures deduced from NOE experiments of QD-3 and QD-4 as well as X-ray crystallographic analysis of QD-4. See Supporting Information.
26. Basavaiah, D.; Gowriswari, V. V. L.; Bharathi, T. K. Tetrahedron Lett. 1987, 28, 4591-4592.
27. Reaction of racemic 4a with 1a in the presence of QD-4 in DMF at -55°C resulted in no reaction after 1 day. At room temperature, very small production of 6 (<3%) was detected after 1 day.
28. 5 it is also assumed that intermediates B and C would be produced selectively from the E-enolate, stabilized by electrostatic interactions, via an open transition state where an aldehyde approaches to the re-face or si-face of the E-enolate.
29. Deslongchamps, P. Stereoelectronic Effects in Organic Chemistry, Pergamon: Oxford, 1983; pp 252-257.