The Journal of Organic Chemistry
NOTE
Scheme 5a
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: viktor.iaroshenko@uni-rostock.de; peter.langer@
uni-rostock.de.
’ ACKNOWLEDGMENT
Financial support by the State of Mecklenburg-Vorpommern
(scholarship for D. O.) and by the BMBF (Grant No.
03IS2081A, scholarship for habilitation of Dr. V. O. I.) is grate-
fully acknowledged.
’ REFERENCES
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526.
a Reagents and conditions: (i) MeOH, NH3, 20 °C, 24 h.
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Table 4. Synthesis of 1-Deazapurine Nucleosides 22, 23, 24,
and 25
R1
R2
22a
23a
24a
25a
a
b
c
CF3
CF3
CF3
Me
Ph
61
45
67
96
97
97
75
79
66
95
94
93
CF3
a Yields of isolated products.
and TMSOTf (0.25 equiv) was added, and the reaction mixture was
refluxed for 2 h (until the color of the solution became yellow-orange).
The solvent and liquid byproducts were evaporated to dryness, and the
residue was purified by column chromatography (EtOAc/heptane = 1:2,
then 1:1) to give the desired glycosylated product as white oil.
Spectral Data for the Compound 1-(2,3,5-Tri-O-acetyl-β-D-
ribofuranosyl)-7-(trifluoromethyl)-5-phenyl-3H-imidazo-
[4,5-b]pyridine (14b): White oil, yield 45%, Rf (EtOAc/heptane,
1:1) = 0.55; 1H NMR (300.13 MHz, CDCl3) δ = 1.93 (s, 3H, Ac), 2.12
(s, 3H, Ac), 2.18 (s, 3H, Ac), 4.34 (dd, 1H, ꢀCH2ꢀ, J1 = 6.0 Hz, J2 = 3.0
Hz), 4.47 (br m, 2H, ꢀCH2ꢀ, H-50), 5.85 (t, 1H, H-40, 3J = 5.1 Hz), 6.21
(t, 1H, H-30, 3J = 5.1 Hz), 6.31 (d, 1H, H-20, 3J = 4.8 Hz), 7.54 (br m, 3H,
Ph), 7.98 (s, 1H, H-5), 8.10 (d, 2H, Ph, 3J = 9.3 Hz), 8.90 (s, 1H, H-2);
13C NMR (62.9 MHz, CDCl3) δ = 20.4 (CH3ꢀCO), 20.5 (CH3ꢀCO),
20.5 (CH3ꢀCO), 62.6 (ꢀCH2ꢀ), 70.1 (C-50), 73.1 (C-40), 79.9 (C-30),
(4) Silverman, R. B. The Organic Chemistry of Drug Design, And Drug
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945. (c) Carlow, D. C.; Carter, C. W., Jr.; Mejlhede, N.; Neuhard, J.;
Wolfenden, R. Biochemistry 1999, 38, 12258–12265.
87.3 (C-20), 112.8 (C-5, t, 3J(CꢀF) = 3.0 Hz), 122.6 (CF3, q, 1J(CꢀF)
=
272.4 Hz), 127.5 (C-400), 129.1 (C-300, C-500), 129.6 (C-200, C-600), 129.8
2
(C-4, q, J(CꢀF) = 29.1 Hz), 131.0 (C-100), 138.2 (C-6), 144.7 (C-2),
(6) (a) Erion, M. D.; Reddy, M. R. J. Am. Chem. Soc. 1998, 120,
3295–3304.
147.6 (C-3a), 154.1 (C-7a), 169.4 (CdO), 169.5 (CdO), 170.4
(CdO); MS (GS) 521 (32) [(M þ H)þ], 306 (10), 259 (79), 244
(10), 157 (14), 139 (100), 97 (42), 43 (78); HRMS (ESI) calcd for
C24H23F3N3O7 (M þ H)þ 521.1489, found 522.1485; IR (ATR) ν =
(7) Begue, J.-P.; Bonnet-Delpon, D. Chemie Bioorganique Et Medic-
inal Du Fluor; EDP Sciences, 2005; p 366, ISBN 2-86883-757-3.
(b) Kirsch, P. Modern Fluoroorganic Chemistry; VCH: Weinheim,
Germany, 2004. (c) Chambers, R. D. Fluorine in Organic Chemistry;
Blackwell Publishing CRC Press: Boca Raton, FL, 2004.
1721, 1630, 1589, 1463, 1402, 1359, 1242, 1056, 761, 623 cmꢀ1
.
(8) (a) Hedstrom, L. Chem. Rev. 2009, 109, 2903–2928. (b)
Markham, G. D.; Bock, C. L.; Schalk-Hihi, C. Biochemistry 1999, 38,
4433–4440.
(9) “De novo” see for example: (a) Rolfes, R. J. Biochem. Soc. Trans.
2006, 34, 786–790. (b) Christopherson, R. J.; Lyons, S. D.; Wilson, P. K.
Acc. Chem. Res. 2002, 35, 961–971. (c) Zalkin, H.; Dixon, J. E. Prog.
Nucleic Acid Res. Mol. Biol. 1992, 42, 259–287.
’ ASSOCIATED CONTENT
S
Supporting Information. Synthetic procedures, com-
b
pound characterization, copies of NMR spectra, X-ray structure.
This material is available free of charge via the Internet at http://
pubs.acs.org.
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dx.doi.org/10.1021/jo102579g |J. Org. Chem. 2011, 76, 2899–2903