7602
I.E. Valverde et al. / Tetrahedron 65 (2009) 7597–7602
JCH2–NH¼5.0 Hz, Hf or Hc), 8.58 (s, 1H, Hf0), 8.07 (d, 1H, JH2–NH
¼
6. Application to multi-triazolo dendrimers: (a) Wu, P.; Feldman, A. K.; Nugent, A.
´
K.; Hawker, C. J.; Scheel, A.; Voit, B.; Pyun, J.; Frechet, J. M. J.; Sharpless, K. B.;
9.0 Hz, NHAc), 8.049 (s, 0.53H, HhM or HaM), 8.035 (s, 0.47H, Hhm or
Fokin, V. V. Angew. Chem., Int. Ed. 2004, 43, 3928–3932; (b) Ornelas, C.; Ruiz
Aranzaes, J.; Cloutet, E.; Alves, S.; Astruc, D. Angew. Chem., Int. Ed. 2007, 46, 872–
0
0
0
Ham), 7.86 (br d, 2H, JHg –Hh ¼7.5 Hz, Hg0), 7.85 (s, 1H, Ha or Hh), 7.45
0
0
0
0
0
¨
877; (c) Antoni, P.; Nystrom, D.; Hawker, C. J.; Hult, A.; Malkoch, M. Chem.
(br dd, 2H, JHh –Hi wJHh –Hg ¼7.5 Hz, Hh ), 7.34 (t, 1H, Hi ), 7.25 (br t,
Commun. 2007, 2249–2251.
2H, JHl–Hk¼JHl–Hm¼7.0 Hz, Hl), 7.19 (t, 1H, Hm), 7.17 (br d, 2H, Hk),
7. Application to multi-triazolo block copolymers: (a) Opsteen, J. A.; van Hest, J.
C. M. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 2913–2924; (b) Johnson, J.
A.; Finn, M. G.; Koberstein, J. T.; Turro, N. J. Macromolecules 2007, 40,
3589–3598.
8. (a) Li, Y.; Flood, A. H. Angew. Chem., Int. Ed. 2008, 47, 2649–2652; (b) Spruell, J.
M.; Dichtel, W. R.; Heath, J. R.; Stoddart, J. F. Chem.dEur. J. 2008, 14,
4168–4177.
9. Applications to multi-triazolo foldamers: (a) Angelo, N. G.; Arora, P. S. J. Org.
Chem. 2007, 72, 7963–7967; (b) Juwarker, H.; Lenhardt, J.; Pham, D. M.; Craig, S.
L. Angew. Chem., Int. Ed. 2008, 47, 3740–3743.
10. For triazole-linked oligosaccharides see: Cheshev, P.; Marra, A.; Dondoni, A. Org.
Biomol. Chem. 2006, 3225–3227.
6.083 (d, 0.53H, JH1–H2¼9.5 Hz, H1M), 6.078 (d, 0.47H, JH1–H2
¼
9.5 Hz, H1m), 5.72 (br dd, 1H, JHe–Hd¼7.5 Hz, He), 5.352 (dd, 0.53H,
H3–H4wJH3–H2¼9.5 Hz, H3M), 5.347 (dd, 0.47H, JH3-H4wJH3-H2
J
¼
9.5 Hz, H3m), 5.065 (dd, 0.53H, JH4–H5¼9.5 Hz, H4M), 5.059 (dd,
0.47H, JH4–H5¼9.5 Hz, H4m), 4.55 (br t, 1H, JHi–Hj¼7.0 Hz, Hi), 4.57–
4.48 (m, 1H, H2), 4.35–4.16 (m, 3H, Hb or Hg, H5), 4.31 (br t, 2H, Hg
or Hb), 4.128 (dd, 0.53H, JH6a–H5¼5.0 Hz, JH6a–H6b¼12.0 Hz, H6aM),
4.122 (dd, 0.47H, JH6a–H5¼5.0 Hz, JH6a–H6b¼12.0 Hz, H6am), 4.01 (br
dd, 1H, JH6b–H5¼7.0 Hz, H6b), 3.17 (br dd, 1H, JHda–Hdb¼16.0 Hz,
Hda), 3.12–3.06 (m, 1H, Hdb), 3.11 (t, 2H, Hj), 2.01 (s, 3H, AcO), 1.97
(s, 3H, AcO), 1.94 (s, 3H, AcO),1.58 (s, 3H, AcNH). 13C NMR (125 MHz,
11. For applications in peptide chemistry see: (a) Franke, R.; Doll, C.; Eichler, J.
Tetrahedron Lett. 2005, 46, 4479–4482; (b) Holub, J. M.; Jang, H.; Kirshenbaum,
K. Org. Biomol. Chem. 2006, 1497–1502; (c) Ku¨min, M.; Sonntag, L.-S.; Wen-
nemers, H. J. Am. Chem. Soc. 2007, 129, 466–467.
(CD3)2SO):
d 170.0 (C), 169.6 (C), 169.51 and 169.50 (CO), 169.3 (C),
12. For applications in glycopeptide chemistry, see: Kuijpers, B. H. M.; Groothuys,
S.; Hawner, C.; ten Dam, J.; Quaedflieg, P. J. L. M.; Schoemaker, H. E.; van Delft, F.
L.; Rutjes, F. P. J. T. Org. Process Res. Dev. 2008, 12, 503–511.
13. For triazole-linked oligonucleotides see: (a) Nuzzi, A.; Massi, A.; Dondoni, A.
QSAR Comb. Sci. 2007, 26, 1191–1199; (b) Lucas, R.; Zerrouki, R.; Granet, R.;
Krausz, P.; Champavier, Y. Tetrahedron 2008, 64, 5467–5471; (c) Isobe, H.; Fu-
jino, T.; Yamazaki, N.; Guillot-Nieckowski, M.; Nakamura, E. Org. Lett. 2008, 10,
3729–3732.
168.0 and 167.9 (CO), 167.10 and 167.08 (CO), 146.1 (C), 144.8 (C),
144.0 (C), 137.6 (C), 130.6 (C), 128.9 (CH), 128.6 (CH), 128.4 (CH),
127.9 (CH), 126.6 (CH), 125.1 (CH), 122.8 (CH), 121.65 and 121.57
(CH), 121.05 (CH), 120.99 (CH), 84.6 (CH), 73.4 (CH), 72.4 (CH), 68.0
(CH), 61.8 (CH2), 59.6 (CH), 52.2 (CH), 50.4 (CH2), 36.9 (CH2), 35.7
(CH2), 34.7 (CH2), 34.1 (CH2), 22.4 (CH3), 20.5 (CH3), 20.4 (CH3), 20.3
(CH3). ESI-HRMS: M¼855.3546 (calcd for C40H47N12O10, 855.3538).
14. Wu, P.; Chen, X.; Hu, N.; Tam, U. C.; Blixt, O.; Zettl, A.; Bertozzi, C. R. Angew.
Chem., Int. Ed. 2008, 47, 5022–5025.
15. (a) Rodionov, V. O.; Fokin, V. V.; Finn, M. G. Angew. Chem., Int. Ed. 2005, 44,
2210–2215; (b) Burley, G. A.; Gierlich, J.; Mofid, M. R.; Nir, H.; Tal, S.; Eichen;
Carell, T. J. Am. Chem. Soc. 2006, 128, 1398–1399; (c) Kalisiak, J.; Sharpless, K. B.;
Fokin, V. V. Org. Lett. 2008, 10, 3171–3174; (d) Pourceau, G.; Meyer, A.; Vasseur,
J.-J.; Morvan, F. J. Org. Chem. 2009, 74, 1218–1222.
16. Hughes simultaneously reported a similar strategy based on a TMS protection:
Montagnat, O. D.; Lessene, G.; Hughes, A. B. Tetrahedron Lett. 2006, 47,
6971–6974.
Acknowledgements
´
I.E.V. thanks the Region Centre Council for a PhD fellowship. This
work was supported by grants from ARC Grand-Ouest, Fondation
pour la Recherche Medicale (comite du Loiret) and La Ligue Contre
´
´
´
le Cancer (comite du Loiret). We are grateful to Guillaume Gabant
17. Goddard-Borger, E. D.; Stick, R. V. Org. Lett. 2007, 9, 3797–3800 and references
cited therein.
18. Aucagne, V.; Leigh, D. A. Org. Lett. 2006, 8, 4505–4507.
19. (a) Orsini, A.; Viterisi, A.; Bodlenner, A.; Weibel, J.-M.; Pale, P. Tetrahedron Lett.
2005, 46, 2259–2262; (b) Carpita, A.; Mannocci, L.; Rossi, R. Eur. J. Org. Chem.
2005, 1859–1864.
`
(CBM) and Bertand Legeret (CRMP, Aubiere) for recording the MS
spectra and to Herve Meudal for recording the NMR spectra. We
thank Dr. Drew Thomson for proofreading the manuscript.
´
20. Ito, H.; Arimoto, K.; Sensui, H.-o; Hosomi, A. Tetrahedron Lett. 1997, 38,
3977–3980.
Supplementary data
21. Meudtner, R. M.; Ostermeier, M.; Goddard, R.; Limberg, C.; Hecht, S. Chem.dEur.
J. 2007, 13, 9834–9840.
22. Gramlich, P. M. E.; Warncke, S.; Gierlich, J.; Carell, T. Angew. Chem., Int. Ed. 2008,
47, 3442–3444.
23. Li, Y.; Flood, A. H. J. Am. Chem. Soc. 2008, 130, 12111–12122.
24. Wuts, P. G. M.; Greene, T. W. Protective Groups in Organic Synthesis, 4th ed.;
Wiley-Interscience: Hoboken, NJ, 2007, Chapter 8.
25. Corriu, R. J. P.; Huynh, V.; Iqbal, J.; Moreau, J. J. E.; Vernhet, C. Tetrahedron 1992,
48, 6231–6244.
Detailed experimental procedures for the reactions listed in
Table 1, kinetic curves from the selective deprotections depicted in
Part 2.4, copies of the 1H and 13C HPLC traces for crude 5–9. Sup-
plementary data associated with this article can be found in the
26. Halbes-Le´tinois, U.; Vasiliev, A.; Pale, P. Eur. J. Org. Chem. 2005, 2828–2834.
27. Bohner, T. V.; Beaudegnies, R.; Vasella, A. Helv. Chim. Acta 1999, 82, 143–160.
28. Manini, P.; Amrein, W.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. 2002,
41, 4339–4343.
References and notes
1. Huisgen, R. Pure Appl. Chem. 1989, 61, 613–628.
29. Source: Beilstein 2008/4 database.
30. Tanigushi, Y.; Inananga, J.; Yamagushi, M. Bull. Chem. Soc. Jpn. 1981, 54, 3229–
3230.
2. Tornøe, C. W.; Meldal, M. In Peptides: The Wave of the Future; Lebl, M.,
Houghten, R. A., Eds.; American Peptide Society and Kluwer Academic: San
Diego, CA, 2001; pp 263–264.
31. Similar results were obtained when using other alcohols as solvents and/or
other bases such as DBU.
32. Lundquist, J. T., IV; Pelletier, J. C. Org. Lett. 2001, 3, 781–783.
33. MacMillan, D.; Daines, A. M.; Bayrhuber, M.; Flitsch, S. L. Org. Lett. 2002, 4,
1467–1470.
3. Tornøe, C. W.; Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057–3064.
4. Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem., Int. Ed.
2002, 41, 2596–2599.
5. See for example: (a) Bock, V. D.; Speijer, D.; Hiemstra, H.; van Maarseveen, J. H.
Org. Biomol. Chem. 2007, 5, 971–975; (b) Appendino, G.; Bacchiega, S.; Minassi,
A.; Cascio, M. G.; De Petrocellis, L.; Di Marzo, V. Angew. Chem., Int. Ed. 2007, 46,
9312–9315.
34. Smith, P. A. S.; Brown, B. B. J. Am. Chem. Soc. 1951, 73, 2435–2437.
35. Walters, M. A.; Hoem, A. B.; McDonough, C. S. J. Org. Chem. 1996, 61, 55–62.