Efficient kinetic resolution in the asymmetric hydrosilylation of imines of 3-substituted indanones and 4-substituted tetralones

Journal of Organic Chemistry

Volumn 65, Issue 3, 2000, Pages 767-774

  Yun, Jaesook ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

IMINE; INDANONE DERIVATIVE; SERTRALINE;

ARTICLE; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHIRALITY; ENANTIOMER; HYDROLYSIS; KINETICS; REACTION ANALYSIS; STEREOISOMERISM; SYNTHESIS;

IMINES; KETONES; KINETICS; N-ACETYLNEURAMINIC ACID; SERTRALINE; SPECTRUM ANALYSIS; STEREOISOMERISM;

EID: 0033968416     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991328h     Document Type: Article

References (52)

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10. For enzymatic kinetic resolutions of 2-substituted indanones or tetralones, see: (a) Adam, W.; Díaz, M. T.; Fell, R. T.; Saha-Möller, C. R. Tetrahedron: Asymmetry 1996, 7, 2207. (b) Kajiro, H.; Mitamura, S.; Mori, A.; Hiyama, T. Tetrahedron: Asymmetry 1998, 9, 907. For nonenzymatic kinetic resolutions of 2-substituted tetralones, see: (c) Genêt, J. P.; Pfister, X.; Ratovelomanana-Vidal, V.; Pinel, C.; Laffitte, J. A. Tetrahedron Lett. 1994, 35, 4559. (d) Kabuto, K.; Ziffer, H. J. Org. Chem. 1975, 40, 3467. (e) Schmalz, H.-G.; Jope, H. Tetrahedron 1998, 54, 3457. (f) Sugi, K. D.; Nagata, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1996, 1081.
11. For enzymatic kinetic resolutions of 2-substituted indanones or tetralones, see: (a) Adam, W.; Díaz, M. T.; Fell, R. T.; Saha-Möller, C. R. Tetrahedron: Asymmetry 1996, 7, 2207. (b) Kajiro, H.; Mitamura, S.; Mori, A.; Hiyama, T. Tetrahedron: Asymmetry 1998, 9, 907. For nonenzymatic kinetic resolutions of 2-substituted tetralones, see: (c) Genêt, J. P.; Pfister, X.; Ratovelomanana-Vidal, V.; Pinel, C.; Laffitte, J. A. Tetrahedron Lett. 1994, 35, 4559. (d) Kabuto, K.; Ziffer, H. J. Org. Chem. 1975, 40, 3467. (e) Schmalz, H.-G.; Jope, H. Tetrahedron 1998, 54, 3457. (f) Sugi, K. D.; Nagata, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1996, 1081.
12. For enzymatic kinetic resolutions of 2-substituted indanones or tetralones, see: (a) Adam, W.; Díaz, M. T.; Fell, R. T.; Saha-Möller, C. R. Tetrahedron: Asymmetry 1996, 7, 2207. (b) Kajiro, H.; Mitamura, S.; Mori, A.; Hiyama, T. Tetrahedron: Asymmetry 1998, 9, 907. For nonenzymatic kinetic resolutions of 2-substituted tetralones, see: (c) Genêt, J. P.; Pfister, X.; Ratovelomanana-Vidal, V.; Pinel, C.; Laffitte, J. A. Tetrahedron Lett. 1994, 35, 4559. (d) Kabuto, K.; Ziffer, H. J. Org. Chem. 1975, 40, 3467. (e) Schmalz, H.-G.; Jope, H. Tetrahedron 1998, 54, 3457. (f) Sugi, K. D.; Nagata, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1996, 1081.
13. For enzymatic kinetic resolutions of 2-substituted indanones or tetralones, see: (a) Adam, W.; Díaz, M. T.; Fell, R. T.; Saha-Möller, C. R. Tetrahedron: Asymmetry 1996, 7, 2207. (b) Kajiro, H.; Mitamura, S.; Mori, A.; Hiyama, T. Tetrahedron: Asymmetry 1998, 9, 907. For nonenzymatic kinetic resolutions of 2-substituted tetralones, see: (c) Genêt, J. P.; Pfister, X.; Ratovelomanana-Vidal, V.; Pinel, C.; Laffitte, J. A. Tetrahedron Lett. 1994, 35, 4559. (d) Kabuto, K.; Ziffer, H. J. Org. Chem. 1975, 40, 3467. (e) Schmalz, H.-G.; Jope, H. Tetrahedron 1998, 54, 3457. (f) Sugi, K. D.; Nagata, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1996, 1081.
14. For enzymatic kintetic resolution of 4-substituted tetralones, see: Bégué, J.-P.; Cerceau, C.; Dogbeavou, A.; Mathé, L.; Sicsic, S. J. Chem. Soc., Perkin Trans. 1 1992, 3141.
15. (a) Carter, M. B.; Schiøtt, B.; Gutiérrez, A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 11667.
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18. (b) Verdaguer, X.; Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed. Engl. 1998, 37, 1103.
19. For an example of kinetic resolution of acylic imines, see: Lensink, C.; de Vries, J. G. Tetrahedron: Asymmetry 1993, 4, 215.
20. (a) Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 11703.
21. (b) We began this project by investigating the kinetic resolution of 3-methylindanone using 1 under hydrosilylation conditons; however, the results were not promising. The recovered ketone was essentially racemic and the diastereomeric alcohol products were produced in a ∼1:1 ratio.
22. For examples of highly efficient kinetic resolution processes using (EBTHI)Zr derivatives, see: Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1262.
23. The selectivity factor, s, was calculated by the equation published in: Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237.
24. The starting acyclic imines were unstable and could not be isolated by the usual separation procedure. Therefore, they were isolated as the corresponding ketones after hydrolysis with HOAc/NaOAc buffer solution or silica gel chromatography.
25. 3, the reaction went to completion at room temperature in 3 h. The distereomeric ratio of the amine products was 77:23 and the ee's of the products were 27% and 91% respectively.
26. 3 at -45°C there was no product formation after 15 h. When the reaction was warmed to -30 °C, it gave 19% conversion in 12 h.
27. With diphenylsilane (3 equiv) as the silane source (2 mol % catalyst) we observed 8% conversion at room temperature in 24 h.
28. 3a
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33. Quallich, G. J.; Williams, M. T.; Friedmann, R. C. J. Org. Chem. 1990, 55, 4971.
34. An experiment with equal amounts of 7b (0.5 mmol) and 10 (0.5 mmol) using 2 mol % catalyst and phenylsilane (2 equiv) was carried out. In 4 h, both substrates reached ∼50% conversion, and the conversion had not increased after an additional 11 h (7b is one of the fast reacting substrate in Table 3).
35. While the resolution of this crystal structure was not high, it was sufficient to show that the methyl group is in an anti position.
36. Guetté, J.-P.; Horeau, A. Bull. Soc. Chim. Fr. 1967, 1747.
37. (a) El-Baba, S.; Poulin, J.-C.; Kagan, H. B. Tetrahedron 1984, 40, 4275.
38. 3 represent the fractional amounts after partial conversion of 1 mol of a compound. C: fractional conversion of one mole of the initial mixture. The asymmetric centers created are labeled R′ or S′. The stereochemical assignment of the equations in the original paper has been modified to that of Figure 1 (R = Me).
39. The ee's of the minor trans-amine products were determined for 6a and 6b. For the imines of indanones 5a and 5b, the higher the conversion, the lower the ee of the cis-amine and the higher the ee of the trans-amine. From this information, the absolute configuration of the minor amine product of 6a was determined as 1R,3R; see Figure 1.
40. 24 For data in Table 2: 3a, 92/91.8, 93/93.9, 86/87.9; 3b, 83/83.9. For data in Table 3: 8a, 96/94.5, 99/100; 8c, 89/89.4, 75.5/74.
41. Equation 1 in ref 24 was used.
42. Equations 5 and 6 in ref 24 were used.
43. 3 in benzene, see: Koelsch, C. F.; Hochmann, H.; Le Claire, C. D. J. Am. Chem. Soc. 1943, 65, 59.
44. Yamamoto, K.; Ogura, H.; Jukuta, J.; Inoue, H.; Hamada, K.; Sugiyama, Y.; Yamada, S. J. Org. Chem. 1998, 63, 4449.
45. Wotiz, J. H.; Matthews, J. S.; Greenfield, H. J. Am. Chem. Soc. 1953, 75, 6342.
46. 3b the cyclization did not proceed to completion.
47. The imines of 3-substituted indanones are very sensitive to air and moisture, especially if they are liquids. Therefore, as soon as they were purified by Kugelrohr distillation, the products were transferred to a glovebox. All of the prepared imines were stored in a -40 °C freezer in a glovebox.
48. This procedure was mostly used for experiments with more unstable indanone imines.
49. Meyers, A. I.; Williams, D. R.; Erickson, G. W.; White, S.; Druelinger, M. J. Am. Chem. Soc. 1981, 103, 3082.
50. Many of the minor amine products produced from the kinetic resolution are more polar than the major amine products assumed to be the eis isomer. Therefore, special care must be taken in order to isolate the minor amine products during chromatography. Thus, the diastereomeric ratio of amine products was determined on the crude reaction mixture. The ee of the products was often determined after transformation of the crude mixture of amines to proper derivatives for chiral analysis.
51. The maximum yield is 100% when the amount of (1 - % conversion/100) x (initial mol of the starting imine substrate) is recovered for ketone substrate and (% conversion/100) x (initial mol of the starting imine substrate) for amine products.
52. The imine substrate (0.5 mmol) showed lower solubility than those of the other imine substrates in this work and was not completely soluble in 1.5 mL of THF. However, after its addition to the activated catalyst via pipet and the mixture became homogeneous (0.5 mmol substrate/2.5 mL solvent in total).