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Chem. 1994, 59, 3503–3505; (d) Yashiro, A.; Nishida, Y.; Ohno, M.;
Eguchi, S.; Kobayashi, K. Tetrahedron Lett. 1998, 39, 9031–9034.
7. Bingel, C. Chem. Ber. 1993, 126, 1957–1959.
60 h, column chromatography (SiO2, toluene/AcOEt 7/3) gave 13 (64
mg, 70%) as a dark-red glassy product. 1H NMR (CDCl3, 300 MHz):
2.10 (m, 4H), 2.80 (t, J = 7 Hz, 4H), 4.38 (m, 4H), 5.20 (d, J = 12 Hz,
2H), 5,47 (s, 4H), 5.80 (d, J = 12 Hz, 2H), 7.15 (m, 15H), 7.30 (s, 1H);
13C NMR (CDCl3, 75 MHz): 21.9, 28.1, 49.3, 54.0, 66.2, 67.0, 67.5,
70.7, 120.9, 123.9, 126.8, 128.0, 128.7, 129.1, 130.0, 134.8, 135.8,
136.2, 136.6, 140.0, 140.9, 141.3, 142.3, 143.0, 143.3, 143.6, 143.8,
144.0, 144.2, 144.3, 144.4, 144.7, 145.0, 145.2, 145.3, 145.4, 145.7,
145.8, 145.8, 146.1, 146.8, 147.4, 147.6, 148.6, 162.8, 162.9; Anal.
Calcd for C98H36N6 O8ꢀ4.8CH2Cl2: C, 67.36; H, 2.51; N 4.50. Found:
C, 67.43; H, 2.93; N, 4.52; MALDI-TOF: 1426 (MH+, calcd for
C98H37N6O8, 1426.41).
8. To a mixture of 4 (92 mg, 0.096 mmol) and benzyl azide (39 mg, 0.293
mmol) in CH2Cl2 (2 mL) and H2O (2 mL) were added CuSO4ꢀ5H2O
(2 mg, 0.012 mmol) and sodium ascorbate (6 mg, 0.030 mmol). The
reaction mixture was stirred for 96 h under N2. The organic layer was
diluted with CH2Cl2, washed with water, dried over MgSO4, and
concentrated. Column chromatography (SiO2, toluene/AcOEt 7/3)
gave 5 (75 mg, 48%) as a dark red glassy product. IR (neat): 1738
(C@O); 1H NMR (CDCl3, 300 MHz): 2.22 (m, 4H), 2.85 (t, J = 7 Hz,
4H), 4.52 (t, J= 6 Hz, 4H), 5.48 (s, 4H), 7.29 (m, 12H); 13C NMR
(CDCl3, 75 MHz) 22.1, 28.1, 50.9, 54.0, 66.5, 67.2, 71.5, 121.0, 128.0,
128.7, 129.1, 134.8, 138.9, 140.9, 141.8, 142.2, 142.9, 143.0, 143.1,
143.9, 144.5, 144.6, 144.7, 144.9, 145.1, 145.2, 145.2, 145.3, 146.8,
163.5; Anal. Calcd for C87H28 N6O4ꢀ4H2O: C, 80.80; H, 2.81; N, 6.50.
Found: C, 81.04; H, 2.94; N, 6.50; FAB-MS: 1221 (M+, calcd for
14. As described for 5 in Ref. 8 from 17 (84 mg, 0.07 mmol), phenylacet-
ylene (15.8 mg, 0.15 mmol), CuSO4ꢀ5H2O (1 mg, 0.006 mmol), and
sodium ascorbate (4 mg, 0.02 mmol) in CH2Cl2 (3 mL) and H2O
(3 mL) for 24 h, columnchromatography (SiO2, CH2Cl2/methanol
99.5/0.5) gave 18 (78%) as a dark orange glassy product. IR (neat):
1742 (C@O);1H NMR (CDCl3, 300 MHz): 2.41 (m, 4H), 4.42 (m,
4H), 4.50 (t, J = 7 Hz, 4H), 5.30 (d, J = 13 Hz, 2H), 5.87 (d,
J = 13 Hz, 2H), 7.30–7.44 (m, 9H), 7.55 (s, 1H), 7.75 (s, 2H), 7.77–
7.84 (m, 4H); 13C NMR (CDCl3, 75 MHz): 29.3, 29.6, 30.9, 46.7, 63.4,
67.7, 119.9, 124.5, 125.7, 127.2, 128.2, 128.8, 130.4, 135.6, 135.8,
136.5, 138.1, 140.1, 141.0, 141.4, 142.3, 142.8, 143.4, 143.6, 143.9,
144.1, 144.2, 144.4, 144.7, 144.9, 145.0, 145.1, 145.3, 145.4, 145.5,
145.7, 145.8, 146.0, 146.1, 146.2, 147.6, 147.9, 148.4, 162.7, 163.0;
Anal. Calcd for C96H32O8N6ꢀCHCl3: C, 76.88; H, 2.20; N, 5.55.
Found: C, 76.31; H, 2.19; N, 5.20; FAB-MS: 1397 (M+, calcd for
C96H32N6O8: 1397.35).
15. As described for 5 in Ref. 8 from 17 (50 mg, 0.031 mmol), 8 (209.4 mg,
0.15 mmol), CuSO4ꢀ5H2O (0.5 mg, 0.003 mmol), and sodium ascor-
bate (2 mg, 0.009 mmol) in CH2Cl2 (1 mL) and H2O (1 mL) for 1 h,
column chromatography (SiO2, CH2Cl2/methanol 99.5/0.5) gave 19
(50%) as a dark red glassy product. IR (neat): 1743 (C@O); 1H NMR
(CDCl3, 300 MHz): 0.87 (t, J = 7 Hz, 12H), 1.24 (m, 72H), 1.56 (m,
8H), 1.72 (m, 8H), 2.20 (m, 4H), 2.35 (m, 4H), 2.86 (t, J = 7 Hz, 4H),
3.87 (t, J = 6 Hz, 8H), 4.38 (m, 4H), 4.42 (t, J = 7 Hz, 4H), 4.50 (t,
J = 6 Hz, 4H), 5.27 (d, J = 13 Hz, 2H), 5.43 (s, 4H), 5.88 (d,
J = 13 Hz, 2H), 6.38 (t, J = 2 Hz, 2H), 6.58 (d, J = 2 Hz, 4H), 7.30–
7.44 (m, 5H), 7.50 (s, 1H); 13C NMR (CDCl3, 75 MHz, d): 14.1, 21.9,
22.6, 26.1, 28.0, 29.2, 29.3, 29.4, 29.6, 29.7, 31.9, 46.5, 49.1, 51.9, 63.4,
66.4, 66.8, 67.7, 68.1, 68.9, 70.5, 71.4, 101.7, 107.2, 121.4, 124.2, 127.1,
128.8, 134.3, 135.7, 136.0, 136.5, 138.0, 138.6, 139.2, 140.1, 140.8,
140.9, 141.0, 141.4, 141.7, 141.8, 142.1, 142.3, 142.8, 142.9, 142.95,
142.97, 142.99, 143.05, 143.3, 143.6, 145.7, 143.8, 143.9, 144.1, 144.2,
144.4, 144.45, 144.5, 144.55, 144.6, 144.62, 144.65, 144.7, 144.8, 144.9,
144.96, 144.97, 145.1, 145.14, 145.19, 145.23, 145.29, 145.5, 145.6,
145.7, 145.9, 146.1, 146.5, 147.3, 147.5, 147.6, 148.4, 160.4, 162.6,
162.9, 163.4; Anal. Calcd for C278H144N6O20ꢀ2CHCl3: C, 81.54; H,
3.57; N, 2.04. Found: C, 81.60; H, 3.15; N, 2.22; FAB-MS: 3889
(MH+, calcd for C278H145N6O20: 3889.24).
C
87H28N6O4, 1221.22).
9. As described for 5 in Ref. 8 from 8 (114 mg, 0.084 mmol), benzyl azide
(22 mg, 0.165 mmol), CuSO4ꢀ5H2O (1 mg, 0.006 mmol), and sodium
ascorbate (4 mg, 0.02 mmol) in CH2Cl2 (2 mL) and H2O (2 mL) for
4 h, column chromatography (SiO2, hexane/CH2Cl2/MeOH 49/49/2)
gave 9 (99 mg, 80%) as a dark red glassy product. IR (neat): 1735
(C@O); 1H NMR (CDCl3, 250 MHz): 0.88 (t, J = 7 Hz, 6H), 1.22–
1.45 (m, 36H), 1.73 (m, 4H), 2.20 (m, 2H), 2.84 (t, J = 7 Hz, 2H), 3.87
(t, J = 7 Hz, 4H), 4.50 (t, J = 6 Hz, 2H), 5.42 (s, 2H), 5.49 (s, 2H),
6.38 (t, J = 2 Hz, 1H), 6.58 (d, J = 2 Hz, 2H), 7.37 (m, 6H); 13C NMR
(CDCl3, 75 MHz): 14.1, 22.1, 22.7, 26.1, 29.3, 29.4, 29.5, 29.6, 29.7,
29.7, 31.9, 51.9, 66.5, 68.2, 68.9, 71.4, 101.6, 107.2, 121.0, 128.0, 128.7,
129.1, 136.8, 138.7, 139.2, 140.8, 141.8, 142.2, 143.0, 143.8, 144.4,
144.5, 144.6, 144.8, 145.0, 145.1, 145.2, 45.3, 160,5, 163.3, 163.3; Anal.
Calcd for C106H69N3O6ꢀ1.3 CH2Cl2: C, 81.05; H, 4.64; N, 2.74.
Found: C, 80.82; H, 4.88; N, 3.00; FAB-MS: 1481 (M+, calcd for
C106H69N3O6, 1480.73).
10. Cardullo, F.; Seiler, P.; Isaacs, L.; Nierengarten, J.-F.; Haldimann, R.
F.; Diederich, F.; Mordasini-Denti, T.; Thiel, W.; Boudon, C.;
Gisselbrecht, J.-P.; Gross, M. Helv. Chim. Acta 1997, 80, 343–371.
11. (a) Nierengarten, J.-F.; Gramlich, V.; Cardullo, F.; Diederich, F.
Angew. Chem., Int. Ed. 1996, 35, 2101–2103; (b) Nierengarten, J.-F.;
Herrmann, A.; Tykwinski, R. R.; Ruttimann, M.; Diederich, F.;
¨
Boudon, C.; Gisselbrecht, J.-P.; Gross, M. Helv. Chim. Acta 1997, 80,
293–316; (c) Nierengarten, J.-F.; Habicher, T.; Kessinger, R.;
Cardullo, F.; Diederich, F.; Gramlich, V.; Gisselbrecht, J.-P.;
Boudon, C.; Gross, M. Helv. Chim. Acta 1997, 80, 2238–2276.
12. Zhang, S.; Rio, Y.; Cardinali, F.; Bourgogne, C.; Gallani, J.-L.;
Nierengarten, J.-F. J. Org. Chem. 2003, 68, 9787–9797. and references
therein.
13. As described for 5 in Ref. 8 from 12 (75 mg, 0.06 mmol), benzyl azide
4
(26 mg, 0.19 mmol) CuSO ꢀ5H2O (1 mg, 0.006 mmol), and sodium
ascorbate (4 mg, 0.02 mmol) in CH2Cl2 (2 mL) and H2O (2 mL) for