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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
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Publication History

Received 22 April 2008
Publication Date:
12 September 2008 (online)

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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

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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.

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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).