140
K. Takatsuki et al. / Tetrahedron Letters 45 (2004) 137–140
Nucleotides 1989, 8, 549–555; (f) Aoyama, H. Bull. Chem.
Soc. Jpn. 1987, 60, 2073–2077.
6a under the similar conditions as for 4 and 5. In con-
trast to the reaction of 4 and 5, the intermediate 20,30-
oxirane, 20,30-anhydro-adenosine 13, was isolated in
83.0% yield (Scheme 3). It is obvious that the cyclo-
sulfinyl group at 30-position is substituted with the 20-
hydroxy group from the a-side. The results indicate the
involvement of the 2030-oxirane intermediates, 11 and 12,
in the rearrangement of 4 and 5, respectively.
9. Rama Rao, A. V.; Gurjar, M. K.; Lalitha, S. V. S.
J. Chem. Soc., Chem. Commun. 1994, 1255–1256.
10. Aman, S.; Anderson, D. J.; Connolly, T. J.; Crittall, A. J.;
Ji, G. Org. Process Res. Develop. 2000, 4, 601–605, and
references cited therein.
11. (a) Nakayama, C.; Saneyoshi, M. Nucleosides Nucleotides
1982, 1, 139–146; (b) Gosselin, G.; Bergogne, M.-C.;
Rudder, J.; De Clercq, E.; Imbach, J.-L. J. Med. Chem.
1986, 29, 203–213; (c) Koshkin, A. A.; Fensholdt, J.;
Pfundheller, H. M.; Lomholt, C. J. Org. Chem. 2001, 66,
8504–8512.
12. Girgis, N. S.; Pedersen, E. B. Synthesis 1982, 480–482.
13. (a) Sowa, T.; Tsunoda, K. Bull. Chem. Soc. Jpn. 1975,
48, 505–507; (b) Sowa, T.; Tsunoda, K. Bull. Chem. Soc.
Jpn. 1975, 48, 3243–3245, They synthesized 20,30-O-sulf-
inate of ribo-nucleosides using thionyl chloride in aceto-
nitrile.
We have established an efficient synthesis of 30-amino-30-
deoxyadenosine 10, 2,20-anhydro-pyrimidine nucleosides
14, and 20,30-anhydro-adenosine 13, which furnishes
puromycine,5 20-deoxy, 20-functional pyrimidine nucleo-
sides,6;9;11;15 and 30-deoxyadenosines.10 Further synthetic
study of puromycin via 6b is now in progress.
14. Murtiashaw, C. W. Eur. Pat. Appl. EP 351,126.
15. (a) Doerr, I. L.; Fox, J. J. J. Org. Chem. 1967, 32, 1462–
1471; (b) Kikugawa, K.; Ichino, M. J. Org. Chem. 1972,
37, 284–288; (c) Wang, M. C.; Sharma, R. A.; Bloch, A.
Cancer Res. 1973, 33, 1265.
References and Notes
€
1. (a) Vorbruggen, H.; Ruh-Pohlenz, C. Handbook of Nucle-
oside Synthesis; John Wiley & Sons, 2001; (b) Ichikawa,
E.; Kato, K. Curr. Med. Chem. 2001, 8, 385–423.
2. Porter, J. N.; Hewitt, R. I.; Hesseltine, C. W.; Krupka, G.;
Lowery, J. A.; Wallace, W. S.; Bohonos, N.; Williams,
J. H. Antibiot. Chemother. 1952, 2, 409–410.
3. (a) Suhadolnik, R. J. Nucleoside Antibiotics; Wiley: New
York, 1970; pp 1–50; (b) Suhadolnik, R. J. Nucleosides as
Biological Probes; Wiley: New York, 1979; pp 96–102.
4. Yarmolinsky, M. B.; De la Haba, G. L. Proc. Natl. Acad.
Sci. U.S.A. 1959, 45, 1721–1729.
5. (a) Robins, M. J.; Miles, R. W.; Samano, M. C.; Kaspar,
R. L. J. Org. Chem. 2001, 66, 8204–8210; (b) Nguyen-
Trung, N. Q.; Botta, O.; Terenzi, S.; Strazewski, P. J. Org.
Chem. 2003, 68, 2038–2041, and references cited therein.
6. (a) McGee, D. P. C.; Zhai, Y. Nucleosides Nucleotides
1996, 15, 1797–1803; (b) Ross, B. S.; Springer, R. H.;
Tortorici, Z.; Dimock, S. Nucleosides Nucleotides 1997,
16, 1641–1643; (c) Saroj, R.; Tang, J.-Y. U.S. Patent
5,739,314; (d) Saroj, R.; Tang, J.-Y. Org. Process Res.
Develop. 2000, 4, 170–171; (e) Parmentier, G.; Schmitt,
G.; Dolle, F.; Luu, B. Tetrahedron 1994, 50, 361–5368; (f)
Cordington, J. F.; Doerr, I. L.; Fox, J. J. J. Org. Chem.
1964, 29, 558.
16. 1H, 13C NMR, and mp data were identical with those
of the authentic sample (Sigma–Aldrich).
17. Spectral data of selected compounds: 4a: Mp (4-methyl-2-
pentanone) 185 °C. IR (KBr): m ¼ 3271, 3169, 3043, 1671,
1471, 1415, 1273, 1210 (RO–SO–OR), 1191, 1113, 1089,
1
1010, 833, 768, 715 cmÀ1. H NMR (DMSO-d 6): d 11.41
(s, 1H, NH), 7.61 (d, J ¼ 8:2 Hz, 1H, H-6), 6.27 (d,
J ¼ 4:3 Hz, 1H, H-10), 5.73 (s, 1H, 20-OH), 5.71 (dd,
J ¼ 8:2 and 1.5 Hz, 1H, H-5), 4.91 (dd, J ¼ 13:4 and
1.8 Hz, 1H, H-40), 4.71 (d, J ¼ 2:4 Hz, 1H, H-30), 4.39 (br
s, 1H, H-50), 4.34 (d, J ¼ 13:4 Hz, 1H, H-50), 4.21 (d,
J ¼ 4:3 Hz, 1H, H-20). 13C NMR (DMSO-d 6): d 163.1,
150.4, 139.4, 101.5, 91.0, 78.7, 73.1, 70.5, 55.8. FAB-MS
m=z: 291.0295 ([M+H]þ, C9H11N2O7S requires m=z:
291.0287). 6a: Mp (4-methyl-2-pentanone) 229 °C. 1H
NMR (DMSO-d 6): d 8.22 (s, 1H, 2-H), 8.15 (s, 1H, 8-H),
7.37 (br s, 2H, NH2), 6.48 (d, 1H, J ¼ 4:0 Hz, OH), 6.09
(br s, 1H, H-10), 4.98 (dd, 1H, J ¼ 13:3 and 1.9 Hz, H-40),
4.87 (d, 1H, J ¼ 2:4 Hz, H-30), 4.63 (d, 1H, J ¼ 2:8 Hz,
H-20), 4.51 (d, 1H, J ¼ 1:8 Hz, H-50), 4.36 (d, 1H, 13.1 Hz,
H-50). MS (m=z, %): 314 ([M+H]þ) (100), 165 (15), 120
(35) 89 (56), 77 (50). 7 Mp (4-methyl-2-pentanone) 174 °C.
1H NMR (DMSO-d 6): d 8.23 (t, J ¼ 6:2 Hz, 1H, NH),
8.20 (pseudo-s, 2H, H-2, and H-8), 7.38 (br s, 2H, NH2),
7.29 (m, 5H, Ph-H), 6.25 (d, 1H, J ¼ 1:8 Hz, H-10), 5.48
(s, 1H, H-20), 5.12 (d, 1H, J ¼ 2:4 Hz, H-30), 4.97 (dd, 1H,
J ¼ 13:3 and 2.0 Hz, 1H, H-40), 4.45 (pseudo-s, 1H, H-50),
4.35 (d, J ¼ 13:4 Hz, 1H, H-50), 4.23 (d, J ¼ 6:1 Hz, 2H,
Ph-CH2). 13C NMR (DMSO-d 6): d 156.0, 154.4, 153.0,
149.1, 138.9, 137.7, 128.2, 127.1, 126.9, 118.5, 86.7, 80.4,
72.9, 69.3, 55.4, 44.0. MS (m=z, %): 447 ([M+H]þ) (93),
312 (54), 307 (33), 91 (100), 89 (65).
€
7. (a) Lubini, P.; Zurcher, W.; Egli, M. Chem. Biol. 1994, 1,
39–45; (b) Adamiak, D. A.; Milecki, J.; Popenda, M.;
Adamiak, R. W.; Dauter, Z.; Rypniewski, W. R. Nucleic
Acids Res. 1997, 25, 4599–4607.
8. (a) Hoffer, M.; Duschinsky, R.; Fox, J. J.; Yung, N. J. Am.
Chem. Soc. 1959, 81, 4112–4113; (b) Niedballa, U.;
€
Vorbruggen, H. J. Org. Chem. 1974, 39, 3654; (c)
Skulnick, H. J. Org. Chem. 1978, 43, 3188–3194; (d)
Hubbard, A. J.; Jones, A. S.; Walker, R. T. Nucleic Acids
Res. 1984, 12, 6827–6837; (e) Freskos, J. N. Nucleosides