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Volumn 127, Issue 7, 2005, Pages 2104-2113

Subtilisin-catalyzed resolution of N-acyl arylsulfinamides

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; BENZENE; BIOSYNTHESIS; COMPUTER SIMULATION; CRYSTALLIZATION; HYDROLYSIS; SULFUR;

EID: 13944260776     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja045397b     Document Type: Article
Times cited : (45)

References (75)
  • 1
    • 11944251609 scopus 로고
    • and references therein
    • Carreña, M. C. Chem. Rev. 1995, 95, 1717-1760 and references therein.
    • (1995) Chem. Rev. , vol.95 , pp. 1717-1760
    • Carreña, M.C.1
  • 2
    • 0000825564 scopus 로고
    • Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; John Wiley & Sons: New York
    • Anderson, K. K. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C. J. M., Eds.; John Wiley & Sons: New York, 1988; pp 55-94.
    • (1988) The Chemistry of Sulphones and Sulphoxides , pp. 55-94
    • Anderson, K.K.1
  • 32
    • 13944265128 scopus 로고
    • Roberts, S. M., Ed.; John Wiley & Sons: New York
    • A computer program, Selectivity-KRESH, was used for all calculations. For details, see: Faber, K.; Hönig, H.; Kleewein, A. In Preparative Biotransformations; Roberts, S. M., Ed.; John Wiley & Sons: New York, 1995; pp 0.079-0.084.
    • (1995) Preparative Biotransformations
    • Faber, K.1    Hönig, H.2    Kleewein, A.3
  • 33
    • 13944268402 scopus 로고    scopus 로고
    • Manuscript in preparation
    • 1H NMR and HRMS-EI identified p-toluenesulfinic acid as the primary product in this enzymatic reaction: Mugford, P. F.; Magloire, V. P.; Kazlauskas, R. J. Manuscript in preparation.
    • Mugford, P.F.1    Magloire, V.P.2    Kazlauskas, R.J.3
  • 37
    • 13944276054 scopus 로고    scopus 로고
    • note
    • Based on a limit of detection of 0.1%.
  • 40
    • 13944262275 scopus 로고    scopus 로고
    • note
    • app = 52%) after 6 h. This enzyme was missed in our initial activity screen because it reacted only slowly with the N-chloroacetyl derivative 1c.
  • 41
    • 13944273882 scopus 로고    scopus 로고
    • note
    • The solubility of both 5h and 6h in 10% MeCN/buffer was <5 mM. Organic cosolvents (1,4-dioxane, EtOH, DMSO) or additives (10 mM guanidium chloride) did not significantly improve solubility. Performing the reaction experiment at 50 °C or using a biphasic reaction system with tert-butylmethyl ether also did not increase conversion. Using MeCN or 1.4-dioxane at higher concentrations (20-90%) improved substrate solubility, but did not increase conversion.
  • 44
    • 13944251103 scopus 로고    scopus 로고
    • note
    • 3 was used in place of sodium bis(trimethylsilyl) amide. (R)-5 formed in low yield (3%) and enantiomeric excess (68% ee).
  • 51
    • 13944261337 scopus 로고    scopus 로고
    • note
    • 1 pocket lies on the surface of the protein and the benzyl group is not completely buried, we estimate the energy for this hydrophobic interaction to be 2.7-5.5 kcal/mol.36a,b,37
  • 52
    • 20544433165 scopus 로고
    • Estimated from the van der Waals radii of chlorine (1.75 Å) and hydrogen (1.20 Å) and the O-H bond length (0.96 Å) from: Bondi, A. J. Phys. Chem. 1964, 68, 441-451.
    • (1964) J. Phys. Chem. , vol.68 , pp. 441-451
    • Bondi, A.1
  • 54
    • 13944275352 scopus 로고    scopus 로고
    • note
    • Removal of a hydrogen bond donor or acceptor in an enzyme active site weakens binding by 0.5-1.5 kcal/mol.37 Although the hydrogen bond inventory is zero (i.e., the number of hydrogen bonds is the same for both the free enzyme and the enzyme-substrate complex), hydrogen bonds between an enzyme and substrate increase the entropy due to the release of bound water molecules.
  • 55
    • 13944262979 scopus 로고    scopus 로고
    • note
    • M values for 1h and 1c than for 1a, but low solubility of these substrates (<5 mM) prevented us from testing this prediction.
  • 58
    • 13944282338 scopus 로고    scopus 로고
    • note
    • 1′ pocket.
  • 61
    • 13944273129 scopus 로고    scopus 로고
    • note
    • See Supporting Information for complete molecular modeling details.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.