3
040
D. Luvino et al.
LETTER
+
+
(
(
(
7) Kosiova, I.; Kovackova, S.; Kois, P. Tetrahedron 2007, 63,
12.
8) Gierlich, J.; Burley, G. A.; Gramlich, P. M. E.; Hammond,
D. M.; Carell, T. Org. Lett. 2006, 8, 3639.
9) Bouillon, C.; Meyer, A.; Vidal, S.; Jochum, A.; Chevolot,
Y.; Cloarec, J. P.; Praly, J. P.; Vasseur, J. J.; Morvan, F.
J. Org. Chem. 2006, 71, 4700.
(FAB , NBA): m/z calcd for C H N O Si (M + H ):
3
4
38
5
4
3
608.2693; found: 608.2712.
(2S,3R)-tert-Butyl-2-(benzyloxycarbonylamino)-3-[4-
(pyren-1-yl)-1,2,3-triazol-1-yl]butanoate (Table 1, entry
10): yield: 75%; mp 81–83 °C; [a] +12° (c = 1, CHCl ); Rf
0.10 (n-hexane–EtOAc, 8:2). H NMR (300 MHz, CDCl ):
d = 1.49 (s, 9 H), 1.83 (d, J = 6.8 Hz, 3 H), 4.85–4.89 (dd,
J = 4.8, 8.5 Hz, 1 H), 5.11 (m, 1 H), 5.17 (s, 2 H), 5.90 (d,
J = 8.3 Hz, 1 H), 7.18–7.31 (m, 3 H), 7.76–7.78 (m, 2 H),
2
0
3
1
3
(
(
10) Perez-Balderas, F.; Ortega-Munoz, M.; Morales-Sanfrutos,
J.; Hernandez-Mateo, F.; Calvo-Flores, F. G.; Calvo-Asin, J.
A.; Isac-Garcia, J.; Santoyo-Gonzalez, F. Org. Lett. 2003, 5,
1
3
8.00–8.14 (m, 9 H), 8.67 (d, J = 9.3 Hz, 1 H). C NMR (75
1
951.
MHz, CDCl ): d = 21.4, 27.9, 58.3, 58.8, 84.0, 122.0, 124.7,
3
11) Kuijpers, B. H. M.; Groothuys, S.; Keereweer, A. R.;
Quaedflieg, P.; Blaauw, R. H.; van Delft, F. L.; Rutjes, F.
Org. Lett. 2004, 6, 3123.
124.8, 125.2, 125.4, 126.1, 126.3, 127.2, 127.4, 127.8,
128.1, 128.2, 128.3, 128.5, 128.6, 129.6, 130.9, 131.3,
+
131.4, 139.3, 143.3, 147.2, 155.9, 167.9. MS (ESI ): m/z
+
+
(12) Odlo, K.; Hoydahl, E. A.; Hansen, T. V. Tetrahedron Lett.
(%) = 561 (100) [M + H] . HRMS (ESI ): m/z calcd for
+
2
007, 48, 2097.
13) Chittaboina, S.; Xie, F.; Wang, Q. Tetrahedron Lett. 2005,
6, 2331.
C H N O (M + H ): 561.2502; found: 561.2480.
3
4
33
4
4
(
1-{2¢-Deoxy-4¢-[1-(2¢,3¢,4¢,6¢-tetra-O-benzyl-b-D-gluco-
pyranosyl)[1,2,3]triazol-4-yl]-3¢-O-tert-butyldimethyl-
silyl-b-D-erythrofuranosyl}thymine (Table 1, entry 11):
4
(14) Kacprzak, K. Synlett 2005, 943.
(
15) Feldman, A. K.; Colasson, B.; Fokin, V. V. Org. Lett. 2004,
yield: 80%; mp 80–83 °C; R 0.51 (n-hexane–EtOAc, 5:5).
f
1
6, 3897.
H NMR (300 MHz, CDCl ): d = 0.00 (s, 3 H), 0.05 (s, 3 H),
3
(
(
16) Andersen, J.; Bolvig, S.; Liang, X. F. Synlett 2005, 2941.
17) Barral, K.; Moorhouse, A. D.; Moses, J. E. Org. Lett. 2007,
0.88 (s, 9 H), 1.84 (s, 3 H), 2.34–2.63 (m, 2 H), 3.78–3.89
(m, 2 H), 4.05–4.18 (m, 2 H), 4.47–4.96 (m, 10 H), 5.61 (d,
J = 9.0 Hz, 1 H), 6.53 (t, J = 6.80 Hz, 1 H), 6.92–6.96 (m, 2
H), 7.16–7.33 (m, 20 H), 7.64 (s, 1 H), 7.82 (s, 1 H), 9.10 (br
9, 1809.
(
(
18) Beckmann, H. S. G.; Wittmann, V. Org. Lett. 2007, 9, 1.
19) Nepogodiev, S. A.; Dedola, S.; Marmuse, L.; de Oliveira, M.
T.; Field, R. A. Carbohydr. Res. 2007, 342, 529.
1
3
s, 1 H). C NMR (75 MHz, CDCl ): d = –4.79, –4.76, 12.5,
3
17.9, 25.6, 40.4, 68.3, 73.6, 74.8, 75.2, 75.8, 77.2, 77.5, 78.1,
80.2, 80.9, 85.5, 85.8, 87.6, 111.2, 122.1, 127.7, 127.8,
127.9, 128.0, 128.1, 128.2, 128.4, 128.5, 136.6, 136.8,
(
(
20) Seela, F.; Sirivolu, V. R. Helv. Chim. Acta 2007, 90, 535.
21) Zheng, S. L.; Reid, S.; Lin, N.; Wang, B. H. Tetrahedron
Lett. 2006, 47, 2331.
+
137.6, 138.0, 146.1, 150.6, 163.9. MS (ESI ): m/z (%) =
+
+
(
22) A quick search in the Aldrich catalogue (sigma-aldrich.com)
found 269 commercial alkynes vs. 870 aldehydes.
23) Ohira, S. Synth. Commun. 1989, 19, 561.
916.3 (100) [M + H] . HRMS (ESI ): m/z calcd for
+
C H N O Si (M + H ): 916.4317; found: 916.4327.
5
1
62
5
9
(
(
3¢-[4-(2¢-Deoxy-3¢-O-tert-butyldimethylsilyl-1¢-thyminyl-
24) Muller, S.; Liepold, B.; Roth, G. J.; Bestmann, H. J. Synlett
b-D-erythrofuranos-4¢-yl)-1,2,3-triazol-1-yl]thymidine
1996, 521.
(Table 1, entry 13): yield: 85%; mp 139–140 °C; R 0.09
f
1
(
25) General Experimental Procedure: The aldehyde (2
mmol), 2-oxopropyldiazodimethyl phosphonate (4 mmol)
and K CO (6 mmol) were suspended in MeOH–THF (1:1;
(CH Cl –EtOAc, 5:5). H NMR (300 MHz, CDCl ): d = 0.06
2
2
3
(2 × s, 6 H), 0.87 (s, 9 H), 1.92 (s, 3 H), 1.95 (s, 3 H), 2.33–
2.71 (m, 2 H), 2.94–3.09 (m, 2 H), 3.82–4.12 (m, 2 H), 4.44–
4.46 (m, 1 H), 4.71–4.74 (m, 1 H), 4.97 (d, J = 3.01 Hz, 1 H),
5.43–5.49 (m, 1 H), 6.21 (t, J = 6.55 Hz, 1 H), 6.36 (t, J = 6.4
Hz, 1 H), 7.41 (s, 1 H), 7.65 (s, 1 H), 7.80 (s, 1 H), 8.61 (br
2
3
4
mL) under an argon atmosphere. The reaction mixture was
stirred at r.t. until TLC showed the reaction to be complete
2–24 h, in some cases another 0.5 equiv of the reagent was
(
1
3
needed to reach completion). When the starting aldehyde
was completely converted into the intermediate alkyne, CuI
s, 1 H), 8.64 (br s, 1 H). C NMR (75 MHz, CDCl ): d =
3
4.83, 12.4, 12.5, 14.2, 25.7, 36.5, 39.8, 59.1, 60.6, 61.2, 76.2,
81.0, 85.3, 87.5, 88.4, 111.2, 122.3, 137.6, 137.7, 146.0,
150.6, 150.8, 164.1, 164.2. MS (ESI ): m/z (%) = 618 (100)
[M + H] . HRMS (FAB , NBA): m/z calcd for C H N O Si
(M + H ): 618.2708; found: 618.2682.
(0.4 mmol) and the azide (2 mmol) were added, and the
+
reaction mixture was stirred at r.t. The progress of the
reaction was followed by TLC (2–12 h). The solvents were
removed in vacuo and the residue was dissolved in EtOAc
+
+
2
7
39
7
8
+
(
20 mL) and H O (20 mL). The aqueous layer was washed
(26) Yang, W.; Gao, X.; Wang, B. Boronic Acids; Hall, D. G.,
Ed.; Wiley-VCH: Weinheim, 2005, Chap. 13.
(27) James, T. D. Boronic Acids; Hall, D. G., Ed.; Wiley-VCH:
Weinheim, 2005, Chap. 12.
2
with EtOAc (2 × 20 mL). The organic phase was washed
with a sat. solution of NH Cl (20 mL), brine (20 mL) and
dried over anhyd Na SO . The solvent was removed in
4
2
4
vacuo and the crude product was further purified by column
chromatography (n-hexane–EtOAc).
(28) Luvino, D.; Smietana, M.; Vasseur, J. J. Tetrahedron Lett.
2006, 47, 9253.
Characterization Data for Selected Compounds:
(29) Characterization Data for Selected Compounds: 1-
Benzyl-4-[3-(4,4,5,5-tetramethyl-1,3-dioxa-2-borolan-2-
yl)phenyl]-1,2,3-triazole (Table 2, entry 1): yield: 30%;
1
-{2¢-Deoxy-4¢-[1-(pyren-1-ylmethyl)-1,2,3-triazol-4-yl]-
3
¢-O-tert-butyldimethylsilyl-b-D-erythrofurano-
syl}thymine (Table 1, entry 6): yield: 73%; mp 125–126
white solid; mp 172–173 °C; R 0.24 (n-hexane–EtOAc,
f
1
1
°C; R 0.53 (n-hexane–EtOAc, 5:5). H NMR (300 MHz,
8:2). H NMR (300 MHz, CDCl ): d = 1.22 (s, 12 H), 5.44
(s, 2 H), 7.14–7.33 (m, 5 H), 7.25 (s, 1 H), 7.59 (s, 1 H), 7.64
(m, 1 H), 7.92 (m, 1 H), 7.97 (m, 1 H). C NMR (75 MHz,
f
3
CDCl ): d = 0.03 (s, 3 H), 0.13 (s, 3 H), 0.75 (s, 9 H), 1.69
3
1
3
(s, 3 H), 2.20–2.29 (m, 1 H), 2.48–2.57 (m, 1 H), 4.66–4.68
(
5
m, 1 H), 4.79 (d, J = 2.6 Hz, 1 H), 6.29 (s, 2 H), 6.44 (t, J =
CDCl ): d = 22.6, 52.0, 81.7, 117.4, 125.8, 126.1, 126.4,
3
+
.9 Hz, 1 H), 7.31 (s, 1 H), 7.64 (s, 1 H), 7.99–8.16 (m, 9
126.5, 126.9, 127.8, 129.7, 132.3, 132.5, 146.0. MS (ESI ):
13
+
+
H). C NMR (75 MHz, CDCl ): d = 4.8, 4.9, 12.4, 25.6, 40.4,
m/z (%) = 362.2 (100) [M + H] . HRMS (ESI ): m/z calcd for
3
+
5
1
1
1
2.5, 75.8, 80.8, 85.7, 111.1, 121.7, 122.4, 124.5, 125.0,
25.2, 125.9, 126.1, 126.2, 126.5, 127.2, 127.8, 128.5,
29.3, 129.4, 130.5, 131.2, 132.3, 136.3, 140.0, 150.2,
C H BN O (M + H ): 362.2040; found: 362.2037.
2
1
25
3
2
1-(Pyren-1-ylmethyl)-4-[4-(4,4,5,5-tetramethyl-1,3-
dioxa-2-borolan-2-yl)phenyl]-1,2,3-triazole (Table 2,
+
+
63.4. MS (ESI ): m/z (%) = 608 (100) [M + H] . HRMS
entry 4): yield: 55%; mp 168–170 °C; R 0.14 (n-hexane–
f
Synlett 2007, No. 19, 3037–3041 © Thieme Stuttgart · New York