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Volumn 63, Issue 10, 1998, Pages 3357-3363

Enzymatic Resolution of Aminocyclopentenols as Precursors to D- and L-Carbocyclic Nucleosides

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEOSIDE DERIVATIVE; PENTANOL;

EID: 0032524830     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972265a     Document Type: Article
Times cited : (75)

References (56)
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    • For reviews on carbocyclic nucleoside chemistry, see: (a) Borthwick, A. D.; Biggadike, K. Tetrahedron 1992, 48, 571. (b) Agrofoglio, L.; Suhas, E.; Farese, A.; Condom, R.; Challand, S. R.; Earl, R. A.; Guedj, R. Tetrahedron 1994, 50, 10611. (c) Mansour, T. S.; Storer, R. Curr. Pharm. Des. 1997, 3, 227. (d) Marquez, V. E. In Advances in Antiviral Drug Design; De Clercq, E., Ed.; JAI Press Inc.: Greenwich, CT, 1996; Vol. 2, p 89.
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    • For reviews on carbocyclic nucleoside chemistry, see: (a) Borthwick, A. D.; Biggadike, K. Tetrahedron 1992, 48, 571. (b) Agrofoglio, L.; Suhas, E.; Farese, A.; Condom, R.; Challand, S. R.; Earl, R. A.; Guedj, R. Tetrahedron 1994, 50, 10611. (c) Mansour, T. S.; Storer, R. Curr. Pharm. Des. 1997, 3, 227. (d) Marquez, V. E. In Advances in Antiviral Drug Design; De Clercq, E., Ed.; JAI Press Inc.: Greenwich, CT, 1996; Vol. 2, p 89.
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    • Mansour, T.S.1    Storer, R.2
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    • De Clercq, E., Ed.; JAI Press Inc.: Greenwich, CT
    • For reviews on carbocyclic nucleoside chemistry, see: (a) Borthwick, A. D.; Biggadike, K. Tetrahedron 1992, 48, 571. (b) Agrofoglio, L.; Suhas, E.; Farese, A.; Condom, R.; Challand, S. R.; Earl, R. A.; Guedj, R. Tetrahedron 1994, 50, 10611. (c) Mansour, T. S.; Storer, R. Curr. Pharm. Des. 1997, 3, 227. (d) Marquez, V. E. In Advances in Antiviral Drug Design; De Clercq, E., Ed.; JAI Press Inc.: Greenwich, CT, 1996; Vol. 2, p 89.
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    • The E value was calculated with the program "Selectivity" available at www-orgc.tu-graz.ac.at/programs/enantio/mac/selectiv.hqx. See: (a) Chen, C.-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294. (b) Chen, C. S.; Wu, S.-H.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1987, 109, 2812.
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    • The E value was calculated with the program "Selectivity" available at www-orgc.tu-graz.ac.at/programs/enantio/mac/selectiv.hqx. See: (a) Chen, C.-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294. (b) Chen, C. S.; Wu, S.-H.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1987, 109, 2812.
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    • note
    • (b) Synthesis of (-)-7b from (-)-7d (Scheme 6) gave a standard for determination of the configuration of acetate (-)-7b derived from enzymatic resolution of (±)-6b. Methyl carbamate (+)-6c obtained from enzymatic hydrolysis was transformed to acetate (-)-7b by the synthetic route shown in Scheme 6 in order to determine its absolute configuration.
  • 36
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    • Chirazyme Lipases and Esterases Screening Kit; Boehringer Mannheim
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    • For a review on enzymatic approaches to enantiomerically pure chiral building blocks, see: (a) Santaniello, E.; Ferraboschi, P.; Grisenti, P.; Manzocchi, A. Chem. Rev. 1992, 92, 1071. (b) Boland, W.; Frobl, C.; Lorenz, M. Synthesis 1991, 1049.
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    • Santaniello, E.1    Ferraboschi, P.2    Grisenti, P.3    Manzocchi, A.4
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    • 4243794106 scopus 로고
    • For a review on enzymatic approaches to enantiomerically pure chiral building blocks, see: (a) Santaniello, E.; Ferraboschi, P.; Grisenti, P.; Manzocchi, A. Chem. Rev. 1992, 92, 1071. (b) Boland, W.; Frobl, C.; Lorenz, M. Synthesis 1991, 1049.
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  • 43
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    • note
    • Acetate (±)-7a was subjected to EEAC in aqueous buffer; apparently, insolubility of the substrate prevented hydrolysis from occurring even after addition of 10% MeOH or 10% EtOH (4 days reaction time).
  • 47
    • 0030008191 scopus 로고    scopus 로고
    • 2Ts). We also found that 9 underwent successful Pd(0) coupling with dimethyl malonate (90% yield) and methyl nitroacetate (69% yield) and in one case underwent coupling with Pd(II) (dimethyl malonate, 65% yield). Adenine coupling, however, was not successful under Pd(0)-coupling conditions, possibly indicative of the equilibrium between the closed and open forms of the urethane. This equilibrium has been previously reported with lactone substrates: Aggarwal, V. K.; Monteiro, N.; Tarver, G. J.; Lindell, S. D. J. Org. Chem. 1996, 61, 1192.
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    • note
    • The buffer was prepared by dissolution of 100 g of sodium dihydrogen phosphate monohydrate into 200 mL of distilled water. The pH of the solution was adjusted to 6.9 with the addition of concentrated sodium hydroxide solution, and then the solution was diluted to a final volume of 500 mL.


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