R. J. D. Nairne et al. / Tetrahedron Letters 43 (2002) 2289–2291
2291
Scheme 2. Reagents and conditions: (i) 10% K2CO3(aq.), 52%; (ii) BOCNH(CH2)3NH2, EDC, HOBt, THF, 77%; (iii) NaH, MeCN,
then a-chloro-(3,5-di-O-p-toluoyl)-2-deoxy- -ribose, 90%; (iv) MeONa, MeOH, 77%; (v) TBDMS-Cl, imidazole, DMF, 90%; (vi)
D
HCONH2, MeONa, MeOH, THF, reflux; (vii) NH4F, MeOH, 72% from 13; (viii) POCl3, P(O)(OMe)3, P(O)(OEt)3, then
Bu3NH·P2O7, DMF; (ix) TFA; (x) 6-fluorescein-5-(and 6-)carboxamidohexanoic acid N-hydroxysuccinimidyl ester, DIPEA,
DMSO.
References
5-Ar-H
J=8 Hz, 2, 6-Ar-H
5. Jagdmann, G. E.; Munson, H. R.; Gero, T. W. Synth.
6
), 7.46 (1H, J=2.5 Hz, pyrrole-H
6
), 7.89 (2H, d,
).
6
), 7.94 (2H, d, J=8.4 Hz, 3, 5-Ar-H
6
1. Bergstrom, D. E.; Zhang, P.; Toma, P. H.; Andrews, P. C.;
Nicholls, R. J. Am. Chem. Soc. 1995, 117, 1201.
Commun. 1990, 20, 1203.
6. Nicolaus, R. A.; Mangoni, L. Gazz. Chim. Ital. 1956, 86,
358.
2. Lakes, D.; Guo, M. J.; Brown, D. M.; Salisbury, S. A.;
Smith, C. L.; Felix, I.; Kumar, S.; Nampalli, S.
Nucleosides, Nucleotides Nucleic Acids 2000, 19, 1599.
3. Japanese Patent JP 7-157466.
7. 1H NMR data for the nucleoside 12 (300 MHz, CDCl3): l
1.14 (3H, t, J=7 Hz, CH2CH3
(2H, quintet, J=6.6 Hz, NCH2CH2
ArCH3), 2.36 (3H, s, ArCH3), 2.62 (2H, br m, 2%-CH2
3.11 (2H, app q, J=6.2 Hz, CH2CO), 3.40 (2H, app q,
2NHCO2 Bu), 4.10 (2H, m, CO2CH2CH3),
4.52 (1H, m, 4%-CH), 4.54 (2H, m, 5%-CH2), 5.27 (1H, br s,
CH2NHCO), 5.55 (1H, m, 3%-CH), 5.95 (1H, dd, J=7.5
and 6.3 Hz, 1%-CH), 7.15 (2H, d, J=8.1 Hz, 3,5-ArH), 7.20
(2H, d, J=8.1 Hz, 3,5-ArH), 7.52 (1H, d, J=2.6 Hz,
pyrrole-H), 7.61 (1H, d, J=2.6 Hz, pyrrole-H), 7.82 (2H,
d, J=8.1 Hz, 2,6-Ar-H), 7.85 (2H, d, J=8.1 Hz, 2,6-Ar-
), and 9.71 (1H, br t, NH
6
), 1.36 (9H, s, C(CH
CH2N), 2.33 (3H, s,
),
6 )3), 1.68
4. 1H NMR data for the nucleoside analogue 8 (300 MHz,
6
6
6
6
CDCl3): l 1.20–1.26 (2H, m, CH2
1.45–1.55 (2H, m, CH2), 1.91–1.94 (2H, m, CH2
(2H, app t, CH2NHBOC, J=7 Hz), 2.22 (3H, s, ArCH3
2.39 (3H, s, ArCH3), 2.64 (2H, m, 2%-CH2), 2.95 (2H, dd,
J=6 and 13 Hz, CH2CONH), 3.68 (3H, s, CO2CH3), 4.29
(2H, d, J=6 Hz, NHCH2-pyrrole), 4.47–4.59 (3H, m,
4%-CH2, 5%-CH2), 5.28 (1H, s, br, amide NH), 5.60 (1H, m,
3%-CH), 6.03 (1H, dd, J=7.7 and 6.2 Hz, 1%-CH), 6.67 (1H,
br, amide NH), 6.81 (1H, d, J=2.5 Hz, pyrrole-H), 7.30
(2H, d, J=8 Hz, 3, 5-Ar-H), 7.31 (2H, d, J=8.4 Hz, 3,
6
), 1.33 (9H, s, C(CH3 3
), 2.07
),
6 ) ),
6
6
6
t
J=7 Hz, CH
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
t
H6
6 CO2 Bu).
6