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Volumn 61, Issue 6, 1996, Pages 2158-2163

Crown ethers as regulators of enzymatic reactions: Enhanced reaction rate and enantioselectivity in lipase-catalyzed hydrolysis of 2-cyano-1-methylethyl acetate

Author keywords

[No Author keywords available]

Indexed keywords

AZACROWNS; ENZYMATIC REACTION; HIGH ENANTIOSELECTIVITY; HYDROLYSIS BEHAVIOR; MOLARITY; THIACROWN ETHERS;

EID: 0001319374     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951598+     Document Type: Article
Times cited : (81)

References (39)
  • 1
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    • A preliminary account has appeared: Itoh, T.; Hiyama, Y.; Betchaku, A.; Tsukube, H. Tetrahedron Lett. 1993, 34, 2617.
    • A preliminary account has appeared: Itoh, T.; Hiyama, Y.; Betchaku, A.; Tsukube, H. Tetrahedron Lett. 1993, 34, 2617.
  • 7
    • 22544438945 scopus 로고
    • and references cited therein. For example, see
    • For example, see: Itoh, T.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1991, 56, 1521 and references cited therein.
    • (1991) J. Org. Chem , vol.56 , pp. 1521
    • Itoh, T.1    Takagi, Y.2    Nishiyama, S.3
  • 12
    • 0027990305 scopus 로고
    • Control of enzyme enantioselectivity by pressure change has recently been reported
    • (e) Arroyo, M.; Sinisterra, J. V. J. Org. Chem. 1994, 59, 4410. Control of enzyme enantioselectivity by pressure change has recently been reported.
    • (1994) J. Org. Chem , vol.59 , pp. 4410
    • Arroyo, M.1    Sinisterra, J.V.2
  • 14
    • 76049100665 scopus 로고    scopus 로고
    • 5g were reported as effective additives. (a) Guo, Z.-W.; Sih, C. J. J. Am. Chem. Soc. 1989, 111, 6839.
    • 5g were reported as effective additives. (a) Guo, Z.-W.; Sih, C. J. J. Am. Chem. Soc. 1989, 111, 6839.
  • 20
    • 0028265843 scopus 로고    scopus 로고
    • Bhaskar, Rao A.; Rehman, H.; Krishnakumari, B.; Yadav, J. S. Tetrahedron Lett. 1994, 35, 2611.
    • (g) Bhaskar, Rao A.; Rehman, H.; Krishnakumari, B.; Yadav, J. S. Tetrahedron Lett. 1994, 35, 2611.
  • 23
    • 76049108903 scopus 로고    scopus 로고
    • -3 mmol/g of lipase PS.
    • -3 mmol/g of lipase PS.
  • 25
    • 33845282987 scopus 로고    scopus 로고
    • Chen, C-S.; Wu, S-H.; Girdauskas, G.; Sih, C. J. Ibid. 1987, 109, 2812. The enantiomeric ratio was calculated from E ln[(1 - c)(1 - ee(S)-1)]/ln[(1 - c)(1 + ee(S)-1)], where c means conversion ratio and c ) ee(S)-1/(ee(S)-1 + ee(R)-2).
    • Chen, C-S.; Wu, S-H.; Girdauskas, G.; Sih, C. J. Ibid. 1987, 109, 2812. The enantiomeric ratio was calculated from E ) ln[(1 - c)(1 - ee(S)-1)]/ln[(1 - c)(1 + ee(S)-1)], where c means conversion ratio and c ) ee(S)-1/(ee(S)-1 + ee(R)-2).
  • 26
    • 76049096226 scopus 로고    scopus 로고
    • We have reported the E value of this control experiment as 7-8 based on results of 19F NMR analysis of, -α-methoxy-α- phenyl-α-(trifluoromethlyl)acetate (MTPA ester method).1 GPC analysis of all experiments gave slightly higher E values than those obtained using MTPA ester method.10 In the MTPA ester method, the remaining acetate was first converted to alcohol by LAH reduction and then to the corresponding MTPA ester.5b Since kinetic resolution may occur during the MTPA formation process, capillary GPC analysis provided us highly reliable results
    • 5b Since kinetic resolution may occur during the MTPA formation process, capillary GPC analysis provided us highly reliable results.
  • 28
    • 76049095498 scopus 로고    scopus 로고
    • (S)-28 was derived from (S)-isopropylideneglycerol by a modification of the published method: Miyazaki, T.; Yanagita, S.; Itoh, A.; Okahara, M. Bull. Chem. Soc. Jpn. 1982, 55, 2005. For the method of preparation, see reference 5f.
    • (S)-28 was derived from (S)-isopropylideneglycerol by a modification of the published method: Miyazaki, T.; Yanagita, S.; Itoh, A.; Okahara, M. Bull. Chem. Soc. Jpn. 1982, 55, 2005. For the method of preparation, see reference 5f.
  • 30
    • 0041431921 scopus 로고
    • Patai, S, Rappoport, Z, Eds, John Wiley & Sons: Chichester
    • Goldberg, I. In Crown Ethers and Analogs; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: Chichester, 1989; p 399.
    • (1989) Crown Ethers and Analogs , pp. 399
    • Goldberg, I.1
  • 38
    • 76049102257 scopus 로고    scopus 로고
    • We employed thiacrown 23 as an additive in hydrolysis of 2-substituted-2-propenyl acetates or 1-alkyl-3-cyanopropyl acetates. Hydrolysis rate of all substrates was accelerated by addition of 5 mol % of thiacrown 23, but enantioselectivity strongly depended on the nature of the substrate. Significant enhancement of enantioselectivity was observed when the original E values were from 7 to 15.
    • We employed thiacrown 23 as an additive in hydrolysis of 2-substituted-2-propenyl acetates or 1-alkyl-3-cyanopropyl acetates. Hydrolysis rate of all substrates was accelerated by addition of 5 mol % of thiacrown 23, but enantioselectivity strongly depended on the nature of the substrate. Significant enhancement of enantioselectivity was observed when the original E values were from 7 to 15.


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