PDF herunterladen
Synlett 2008(16): 2491-2494  
DOI: 10.1055/s-2008-1078058
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Novel DNA-Catalyzed Aldol Reaction

Gaojun Suna, Jinmin Fana, Zhiyong Wang*a, Yingfu Li*b
a Hefei National Laboratory for Physical Science at Microscale, Joint-Lab of Green Synthetic Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. of China
Fax: +86(551)3603185; e-Mail: zwang3@ustc.edu.cn;
b Department of Biochemistry and Biomedical Science and Department of Chemistry, McMaster University, Hamilton, ON L8N3Z5, Canada
Weitere Informationen

Publikationsverlauf

Received 22 April 2008
Publikationsdatum:
12. September 2008 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A novel DNA-catalyzed aldol reaction in water has been developed. This approach will be helpful in learning the role of DNA as a catalyst in the early stage during the development of life on earth.

Keywords

DNA - aldol reaction - catalyst - aqueous buffer

    References and Notes

  • 1a Lu Y. Liu JW. Curr. Opin. Biotechnol.  2006,  17:  580 
    Google Scholar
  • 1b Roelfes G. Mol. BioSyst.  2007,  3:  126 
    Google Scholar
  • 1c Scherer LJ. Rossi JJ. Nat. Biotechnol.  2003,  21:  1457 
    Google Scholar
  • 1d Liu JW. Lu Y. J. Fluoresc.  2004,  14:  343 
    Google Scholar
  • 1e Lu Y. Liu JW. Acc. Chem. Res.  2007,  40:  315 
    Google Scholar
  • 1f May JP. Ting R. Lermer L. Thomas JM. Roupioz Y. Perrin DM. J. Am. Chem. Soc.  2004,  126:  4145 
    Google Scholar
  • 1g Isaka Y. Curr. Opin. Mol. Ther.  2007,  9:  132 
    Google Scholar
  • 2a Kanan MW. Rozenman MM. Sakurai K. Snyder TM. Liu DR. Nature (London)  2004,  431:  545 
    Google Scholar
  • 2b Li XY. Liu DR. Angew. Chem. Int. Ed.  2004,  43:  4848 ; and references therein
    Google Scholar
  • 2c Silverman AP. Kool ET. Chem. Rev.  2006,  106:  3775 
    Google Scholar
  • 2d Sakurai K. Snyder TM. Liu DR. J. Am. Chem. Soc.  2005,  127:  1660 
    Google Scholar
  • 2e Obika S. Tomizu M. Negoro Y. Orita A. Nakagawa O. Imanishi T. ChemBioChem  2007,  8:  1924 
    Google Scholar
  • 2f Oberhuber M. Joyce GF. Angew. Chem. Int. Ed.  2005,  44:  7580 
    Google Scholar
  • 3a Miller SJ. Nat. Biotechnol.  2004,  22:  1378 
    Google Scholar
  • 3b Rozenman MM. Liu DR. ChemBioChem  2006,  7:  253 
    Google Scholar
  • 3c Silverman SK. Org. Biomol. Chem.  2004,  2:  2701 
    Google Scholar
  • 3d Gartner ZJ. Liu DR. J. Am. Chem. Soc.  2001,  123:  6961 
    Google Scholar
  • 4a Roelfes G. Feringa BL. Angew. Chem. Int. Ed.  2005,  44:  3230 
    Google Scholar
  • 4b Coquire D. Feringa BL. Roelfes G. Angew. Chem. Int. Ed.  2007,  46:  9308 
    Google Scholar
  • 4c Roelfes G. Boersma AJ. Feringa BL. Chem. Commun.  2006,  635 
    Google Scholar
  • 4d Boersma AJ. Feringa BL. Roelfes G. Org. Lett.  2007,  9:  3647 
    Google Scholar
  • 4e Shibata N. Yasui H. Nakamura S. Toru T. Synlett  2007,  1153 
    Google Scholar
  • 5 Fan JM. Sun GJ. Wan CF. Wang ZY. Li YF. Chem. Commun.  2008,  3792 
    Google Scholar
  • 6 Modern Aldol Reactions   Mahrwald R. Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 7a Zotova N. Franzke A. Armstrong A. Blackmond DG. J. Am. Chem. Soc.  2007,  129:  15100 
    Google Scholar
  • 7b Dipeptide-catalyzed Aldol reactions can be carried out in water-organic solvent mixtures; see: Dziedzic P. Zou W. Háfren J. Córdova A. Org. Biomol. Chem.  2006,  4:  38 
    Google Scholar
  • 7c Font D. Jimeno C. Pericàs MA. Org. Lett.  2006,  8:  4653 
    Google Scholar
  • 7d Fernandez-Lopez R. Kofoed J. Machuqueiro M. Darbre T. Eur. J. Org. Chem.  2005,  5268 
    Google Scholar
  • 7e Chimni SS. Mahajan D. Tetrahedron  2005,  61:  5019 
    Google Scholar
  • 8a List B. Lerner RA. Barba CF. J. Am. Chem. Soc.  2000,  122:  2395 
    Google Scholar
  • 8b Sakthivel K. Notz W. Bui T. Barbas CF. J. Am. Chem. Soc.  2001,  123:  5260 
    Google Scholar
  • 8c Notz W. List B. J. Am. Chem. Soc.  2000,  122:  7386 
    Google Scholar
  • 8d List B. J. Am. Chem. Soc.  2000,  122:  9336 
    Google Scholar
  • 8e Bui T. Barbas CF. Tetrahedron Lett.  2000,  41:  6951 
    Google Scholar
  • 8f Còrdova A. Notz W. Zhong G. Betancort JM. Barbas CF. J. Am. Chem. Soc.  2002,  124:  1842 
    Google Scholar
  • 8g Kumaragurubaran N., Juhl K., Zhuang W., Bøgevig A., Jørgensen K. A.; J. Am. Chem. Soc.; 2002, 124: 6254
  • 8h List B.; J. Am. Chem. Soc.; 2002, 124: 5656
  • 8i Bøgevig A. Juhl K. Kumaragurubaran N. Zhuang W. Jørgensen KA. Angew. Chem. Int. Ed.  2002,  41:  1790 
    Google Scholar
  • 8j Northrup AB. MacMillan DWC. J. Am. Chem. Soc.  2002,  124:  6798 
    Google Scholar
  • 8k Còrdova A. Watanabe S. Tanaka F. Notz W. Barbas CFIII. J. Am. Chem. Soc.  2002,  124:  1866 
    Google Scholar
  • 8l For reviews, see: Chen J.-R. Li X.-Y. Xing X.-N. Xiao W.-J. J. Org. Chem.  2006,  71:  8198 
    Google Scholar
  • 8m List B. Tetrahedron  2002,  58:  5573 
    Google Scholar
  • 8n List B. Synlett  2001,  1675 
    Google Scholar
  • 9a Tang Z. Marx A. Angew. Chem. Int. Ed.  2007,  46:  7297 
    Google Scholar
  • 9b Tang Z. Goncalves DPN. Wieland M. Marx A. Hartig JS. ChemBioChem  2008,  9:  1061 
    Google Scholar
  • 10 Fusz S. Eisenführ A. Srivatsan SG. Heckel A. Famulok M. Chem. Biol.  2005,  12:  941 
    CrossrefPubMedGoogle Scholar
  • 11a Gilbert W. Nature (London)  1986,  319:  618 
    Google Scholar
  • 11b Joyce GF. Nature (London)  2002,  418:  214 
    Google Scholar
12

Typical Procedure for the Aldol Reaction of
p -Nitrobenzaldehyde with Acetone
To an aq MOPS buffer solution (30 mM, pH = 6.50) was added DNA (herring sperm or salmon testes DNA 20 mg, purchased from Sigma). After 10 min, p-nitrobenzaldehyde (0.5 mmol) in acetone (1.5 mL) was added. After the mixture was heated at 40 ˚C for 3.5 d, the mixture was extracted three times with CHCl3. The combined organic extract was dried with anhydrous Na2SO4 and evaporated under reduced pressure; the residue was then purified by column chromatography over SiO2 to afford the corresponding aldol product with high purity.

13

Spectroscopic Data for Products All products are known compounds; see refs. 7d,e and 8a,l. 4-Hydroxy-4-phenylbutan-2-one (2a)
¹H NMR (300 MHz, CDCl3): δ = 7.36-7.27 (m, 4 H), 5.15 (dd, J 1 = 3.6 Hz, J 2 = 8.7 Hz, 1 H), 2.88-2.83 (m, 3 H), 2.19 (s, 3 H).
4-(4-Fluorophenyl)-4-hydroxybutan-2-one (2b) ¹H NMR (300 MHz, CDCl3): δ = 8.04 (d, J = 8.1 Hz, 2 H), 7.03 (t, J = 8.7 Hz, 2 H), 5.13 (t, J = 3.6 Hz, 1 H), 2.83 (d, J = 7.5 Hz, 2 H), 2.20 (s, 3 H). 4-(4-Chlorophenyl)-4-hydroxybutan-2-one (2c)
¹H NMR (300 MHz, CDCl3): δ = 7.32 (t, J = 4.2 Hz, 2 H), 7.46 (d, J = 8.1 Hz, 2 H), 5.14 (t, J = 4.8 Hz, 1 H), 3.38 (d, J = 1.5 Hz, 1 H), 2.85 - 2.81 (m, 2 H), 2.19 (s, 3 H). 4-(4-Bromophenyl)-4-hydroxybutan-2-one (2d) ¹H NMR (300 MHz, CDCl3): δ = 7.47 (d, J = 8.4 Hz, 2 H), 7.23 (d, J = 8.1 Hz, 2 H), 5.10 (d, J = 3.6 Hz, 1 H), 3.41 (s, 1 H), 2.83-2.75 (m, 2 H), 2.19 (s, 3 H). 4-Hydroxy-4-(4-nitrophenyl)butan-2-one (2e) ¹H NMR (300 MHz, CDCl3): δ = 8.21 (d, J = 4.4 Hz, 2 H), 7.54 (d, J = 8.1 Hz, 2 H), 5.27 (dd, J 1 = 4.8 Hz, J 2 = 7.5 Hz, 1 H), 3.57 (s, 1 H), 2.87-2.84 (m, 2 H), 2.23 (s, 3 H). 4-Hydroxy-4-(2-nitrophenyl)butan-2-one (2f) ¹H NMR (300 MHz, CDCl3): δ = 7.96 (d, J = 8.1 Hz, 1 H), 7.90 (d, J = 7.8 Hz, 1 H), 7.67 (t, J = 7.5 Hz, 1 H), 7.44 (t, J = 8.1 Hz, 1 H), 5.68 (d, J = 9.3 Hz, 1 H), 3.65 (s, 1 H), 3.14 (dd, J 1 = 1.5 Hz, J 2 = 17.7 Hz,1 H), 2.72 (dd, J 1 = 9.3 Hz, J 2 = 17.7 Hz, 1 H), 2.24 (s, 3 H).
4-[4-(Trifluoromethyl)phenyl]-4-hydroxybutan-2-one (2g) ¹H NMR (300 MHz, CDCl3): δ = 7.61 (d, J = 7.8 Hz, 2 H), 7.48 (d, J = 7.8 Hz, 1 H), 5.22 (s, 1 H), 2.85 (d, J = 6.0 Hz, 2 H), 2.21 (s, 3 H). 4-Hydroxy-4-(pyridin-2-yl)butan-2-one (2h) ¹H NMR (300 MHz, CDCl3): δ = 8.53 (d, J = 3.9 Hz, 1 H), 7.70 (t, J = 7.5 Hz, 1 H), 7.46 (d, J = 7.5 Hz, 1 H), 7.20 (t, J = 5.1 Hz, 1 H), 5.20 (dd, J 1 = 3.3 Hz, J 2 = 8.1 Hz, 1 H), 4.25 (s, 1 H), 3.05 (dd, J 1 = 3.3 Hz, J 2 = 16.8 Hz, 1 H), 2.91 (dd, J 1 = 8.4 Hz, J 2 = 17.1 Hz, 1 H), 2.22 (s, 3 H). 2-[Hydroxy(4-nitrophenyl)methyl]cyclopentanone (3a) Mixture of syn- and anti-product: ¹H NMR (400 MHz, CDCl3): δ = 8.23-8.19 (m, 4 H), 7.55-7.51 (m, 4 H), 5.42 (d, J = 3.0 Hz, 1 H), 4.85 (d, J = 9.1 Hz, 1 H), 2.48-1.98 (m, 6 H), 1.75-1.55 (m, 2 H). 3,4-Dihydroxy-4-(4-nitrophenyl)butan-2-one (3b) Mixture of syn- and anti-product: ¹H NMR (300 MHz, CDCl3): δ = 8.25 (d, J = 8.4 Hz, 4 H), 7.61 (d, J = 8.4 Hz, 4 H), 5.22 (d, J = 1.3 Hz, 1 H), 5.09 (d, J = 4.5 Hz, 1 H), 4.47 (d, J = 4.5 Hz, 1 H), 4.41 (d, J = 2.1 Hz, 1 H), 3.72 (s, 2 H), 2.36 (s, 3 H), 2.03 (s, 3 H). 4-Hydroxy-3-methyl-4-(4-nitrophenyl)butan-2-one (3c) Mixture of syn- and anti-product: ¹H NMR (300 MHz, CDCl3): δ = 8.21 (d, J = 8.4 Hz, 4 H), 7.52 (d, J = 7.5 Hz, 4 H), 5.28 (s, 1 H), 4.86 (d, J = 1.4 Hz, 1 H), 3.42 (s, 1 H), 2.23 (d, J = 9 Hz, 3 H), 1.11 (s, 3 H), 1.06 (s, 3 H). 2-[Hydroxy(4-nitrophenyl)methyl]cyclohexanone (3d) Mixture of syn- and anti-product: ¹H NMR (300 MHz, CDCl3): δ = 8.21 (d, J = 7.5 Hz, 4 H), 7.50 (dd, J 1 = 6.0 Hz, J 2 = 8.1 Hz, 4 H), 5.49 (s, 1 H), 4.90 (d, J = 8.4 Hz, 1 H), 4.05 (s, 1 H), 3.15 (s, 1 H), 2.64-2.39 (m, 4 H), 2.36-2.09 (m, 2 H), 1.84-1.40 (m, 8 H). Tetrahydro-3-[hydroxy(4-nitrophenyl)methyl]pyran-4-one (3e) Mixture of syn- and anti-product: ¹H NMR (300 MHz, CDCl3): δ = 8.22 (dd, J 1 = 2.1 Hz, J 2 = 8.7 Hz, 4 H), 7.52 (d, J = 8.7 Hz, 4 H), 4.99 (d, J = 7.5 Hz, 1 H), 4.24-4.21 (m, 2 H), 3.87-3.73 (m, 8 H), 3.49-3.46 (m, 1 H), 2.97-2.91 (m, 3 H), 2.57-2.55 (m, 3 H), 2.51-2.45 (m, 3 H).