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Castedo, L.; Granja, J. R. Org. Lett. 2001, 3, 1483–1486;
(c) Kitamura, T.; Mori, M. Org. Lett. 2001, 3, 1161–1163.
14. Stragies, R.; Schuster, M.; Blechert, S. Angew. Chem., Int.
s); 1.08 (tBu(Me), 9H, s). 13C NMR (25 MHz, CDCl3):
144.7 (s), 139.9 (s), 135.5 (d), 133.8 (s), 133.7 (s), 130.8 (d),
130.6 (d), 129.8 (d), 128.6 (d), 127.8 (d), 127.7 (d), 117.3
(t), 68.8 (t), 64.1 (t), 31.7 (t), 26.8 (q), 19.2 (s). APcI (+)
(m/z): 543 (M+Na)+.
Ed. Engl. 1997, 36, 2518–2520.
15. (a) Kinoshita, A.; Sakakibara, N.; Mori, M. J. Am. Chem.
Soc. 1997, 119, 12388–12389; (b) Smulik, J. A.; Diver, S.
T. J. Org. Chem. 2000, 65, 1788–1792.
25. (a) Gurjar, M. K.; Yakambram, P. Tetrahedron Lett. 2001,
42, 3633–3636; (b) Hoye, T. R.; Zhao, H. Org. Lett. 1999,
1, 1123–1125; (c) Couturier, J. L.; Leconte, M.; Basset, J.
M. J. Organomet. Chem. 1993, C7; (d) Wu, Z.; Nguyen,
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16. Zheng, G.; Dougherty, T. J.; Pandey, R. K. Chem. Com-
mun. 1999, 2469–2470.
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Schu¨ster, M.; Blechert, S. Tetrahedron Lett. 1998, 39,
2295–2298; (c) Stragies, R.; Schuster, M.; Blechert, S.
Chem. Commun. 1999, 237–238; (d) Schu¨rer, S. C.;
Blechert, S. Chem. Commun. 1999, 1203–1204; (e) Kotha,
S.; Halder, S.; Brahmachary, E.; Ganesh, T. Synlett 2000,
853–855; (f) Smulik, J. A.; Diver, S. T. Tetrahedron Lett.
2001, 42, 171–174.
1
26. 10Z: H NMR (200 MHz, CDCl3): 7.68 (Ph(Si), 4H, m);
7.39 (Ph(Si), 6H, m); 5.85 (SiOCH2CH, 1H, m); 5.81
(SiOCH2CHCH, 1H, bd); 4.96 (ꢀCH2, 1H, s); 4.67 (ꢀCH2,
1H, s); 4.39 (SiOCH2, 2H, d, J=4.4 Hz); 3.68 (COOCH3,
3H, s); 3.19 (CH2NHCOOCH3, 2H, q, J=6.5 Hz); 2.21
(CH2CH2NH, 2H, t, J=6.5 Hz); 1.08 (tBu(Me), 9H, s). 13
C
NMR: 157.1 (s), 142.3 (s), 135.5 (d), 133.7 (s), 130.9 (d),
130.8 (d), 128.7 (d), 127.7 (d), 116.6 (t), 64.3 (t), 51.9 (q),
39.4 (t), 32.5 (t), 26.8 (q), 19.1 (s). APcI (+) (m/z): 424
(M+H)+. 10E: 1H NMR (200 MHz, CDCl3): 7.68 (Ph(Si),
4H, m); 7.39 (Ph(Si), 6H, m); 6.30 (-SiOCH2CHCH-, 1H,
d, J=16.1 Hz); 5.77 (SiOCH2CH-, 1H, m); 5.06 (ꢀCH2, 1H,
s); 4.97 (ꢀCH2, 1H, s); 4.29 (-SiOCH2-, 2H, d, J=6.3 Hz);
3.65 (-COOCH3-, 3H, s); 3.31 (CH2NHCOOCH3-, 2H, q,
J=6.5 Hz); 2.41 (-CH2CH2NH-, 2H, t, J=6.5 Hz); 1.06
(tBu(Me), 9H, s). 13C NMR: 157.0 (s), 141.6 (s), 135.5 (d),
133.7 (s), 132.8 (d), 130.9 (d), 130.8 (d), 116.6 (t), 61.0 (t),
51.9 (q), 39.4 (t), 37.0 (t), 26.8 (q), 19.1 (s). APcI (+) (m/z):
424 (M+H)+.
18. Nishiguchi, N.; Kinoshita, A.; Mori, M. Tennen Uki
Kagobutsu Toronkai Koen Yoshishu 2000, 42, 739–744.
19. Crews, P.; Kakou, Y.; Quin˜oa´, E. J. Am. Chem. Soc. 1988,
110, 4365–4368.
20. Results of the National Cancer Institute Human Tumor
Cell Line Screen mean graph can be obtained at http://
dtp.nci.nih.gov/, NSC number 647640.
21. Sugiyama, H.; Yokokawa, F.; Shioiri, T. Org. Lett. 2000,
2, 2149–2152.
22. Pe´rez, D.; Bures, G.; Guitian, E.; Castedo, L. J. Org. Chem.
1996, 61, 1650–1654.
23. In the literature there are very few cases using the amines
monoprotected as carbamates or sulfonamides. In these
cases the enyne metathesis proceed in yields in the range
10–56% as in Ref. 17e. Fully functionalized amines gave
better results as in Refs. 15a and 17f.
27. 11Z: 1H NMR (200 MHz, CDCl3): 5.93 (1H,
HOCH2CHCH, d, J=12.1 Hz), 5.79 (1H, HOCH2CHCH,
dt, J=12.1 and 5.9 Hz), 5.10 (1H, ꢀCH2, s); 4.80 (1H,
ꢀCH2, s), 4.70 (bs, NH); 4.28 (2H, HOCH2CH, d, J=5.9
Hz); 3.66 (3H, COOMe, s); 3.32 (2H, CH2NHCOOMe, m);
2.30 (2H, CH2CH2NHCOOMe, t, J=6.3 Hz); 2.20 (bs;
OH). 13C NMR: 157.2 (s), 141.7 (s), 132.3 (d), 130.7 (d),
117.0 (t), 59.1 (t), 52.1 (q), 39.4 (t), 37.6 (t). APcI (+) (m/z):
186 (M+H)+. 11E: 1H NMR (200 MHz, CDCl3): 6.28 (1H,
24. Representative experimental procedure for enyne metathe-
sis: 0.65 g (2.90 mmol) of toluene-4-sulfonic acid but-3-ynyl
ester (7) was dissolved in 5 mL of dry CH2Cl2. 1.72 g (5.80
mmol) of allyloxy-tert-butyl-diphenyl-silane (8) in 2 mL of
CH2Cl2 were added. After addition of 0.238 g (0.290 mmol)
of Grubbs’ catalyst (2) in 8 mL of CH2Cl2, the mixture was
stirred for 8 h at room temperature. Then, 0.19 g (0.435
mmol) of lead tetraacetate in 1 mL of CH2Cl2 was added
and the reaction was stirred for 12 h at rt. The crude was
concentrated under vacuum and purified chromatograph-
ically with hexane:EtOAc (10:1) on silica gel. 1.45 g (95%)
of a mixture E:Z (1.1:1.0, 9) were obtained on the basis
HOCH2CHCH-,
d,
J=16.1
Hz);
5.95
(1H,
HOCH2CHCH-, dt, J=16.1 and 6.8 Hz), 5.12 (1H, ꢀCH2,
s); 5.02 (1H, ꢀCH2, s), 4.70 (bs, NH); 4.23 (2H, HOCH2CH,
d, J=6.8 Hz), 3.66 (3H, COOMe, s); 3.32 (2H,
CH2NHCOOMe,
q,
J=6.8
Hz,);
2.44
(2H,
CH2CH2NHCOOMe, t, J=6.8 Hz); 1.50 (bt; OH). 13C
NMR: 157.2 (s), 141.7 (s), 130.7 (d), 128.6 (d), 117.0 (t),
59.1 (t), 52.1 (q), 39.4 (t), 32.6 (t). APcI (+) (m/z): 186
(M+H)+.
1
1
of the H NMR and H–1H COSY spectra.
9Z: 1H NMR (200 MHz, CDCl3): 7.78 (OTs, 2H, m); 7.68
(Ph(Si), 4H, m); 7.41 (Ph(Si), 6H, m); 7.37 (OTs, 2H, m);
5.76 (SiOCH2CHCH, 1H, m), 5.72 (SiOCH2CHCH, 1H,
bd); 4.91 (ꢀCH2, 1H, s); 4.67 (ꢀCH2, 1H, s); 4.24 (SiOCH2,
2H, bd, J=6.3 Hz); 4.05 (TsOCH2, 2H, t, J=6.8 Hz); 2.43
(TsO, 3H, s); 2.41 (OTs, 3H, s); 2.34 (CH2CH2OTs, 2H,
t, J=6.8 Hz); 1.08 (tBu(Me), 9H, s). 13C NMR (25 MHz,
CDCl3): 144.7 (s), 139.1 (s), 135.5 (d), 133.8 (s), 133.5 (s),
130.8 (d), 130.6 (d), 129.7 (d), 129.6 (d), 127.8 (d), 127.7
(d), 117.4 (t), 68.6 (t), 61.0 (t), 36.1 (t), 26.8 (q), 19.2 (s).
1
28. 4: H NMR (200 MHz, CDCl3): 5.96 (BrCH2CHCH, 1H,
d, J=10.7 Hz); 5.92 (BrCH2CHCH, 1H, dt, J=10.7 Hz
and 7.8 Hz); 5.16 (ꢀCH2, 1H, s); 5.14 (ꢀCH2, 1H, s); 4.12
(BrCH2CHCH, 2H, d, J=7.8 Hz); 3.67 (NHCOOMe, 3H,
s); 3.27 (CH2NHCOOMe, 2H, q, J=6.3 Hz); 2.35
(CH2CH2NH, 2H, t, J=6.3 Hz). 13C NMR: 157.0 (s), 141.0
(s), 133.7 (d), 127.8 (d), 117.2 (t), 52.1 (q), 39.5 (t), 37.1 (t),
28.2 (t). FAB (+) (m/z): 249/251. 4E: 1H NMR (200 MHz,
CDCl3): 6.30 (BrCH2CHCH, 1H, d, J=16.5 Hz); 5.90
(BrCH2CHCH, 1H, dt, J=16.5 Hz and 6.1 Hz); 5.18
(ꢀCH2, 1H, s); 5.05 (ꢀCH2, 1H, s); 4.10 (BrCH2CHCH, 2H,
bd, J=6.1 Hz); 3.67 (NHCOOMe, 3H, s); 3.30
(CH2NHCOOMe, 2H, q, J=6.3 Hz); 2.42 (CH2CH2NH,
2H, t, J=6.3 Hz). 13C NMR: 156.9 (s), 140.9 (s), 135.9 (d),
125.9 (d), 117.2 (t), 52.1 (q), 39.5 (t), 33.0 (t), 29.7 (t). FAB
(+) (m/z): 249/251.
1
APcI (+) (m/z): 543 (M+Na)+. 9E: H NMR (200 MHz,
CDCl3): 7.78 (OTs, 2H, m); 7.68 (Ph(Si), 4H, m); 7.41
(Ph(Si), 6H, m); 7.37 (OTs, 2H, m); 6.23 (SiOCH2CHCH,
1H, d, J=16.1 Hz); 5.62 (SiOCH2CH, 1H, dt, J=16.1 Hz
and 4.7 Hz); 5.13 (ꢀCH2, 1H, s), 5.03 (ꢀCH2, 1H, s); 4.24
(SiOCH2, 2H, bd, J=6.3 Hz); 4.14 (CH2OTs, 2H, t, J=7.3
Hz); 2.57 (CH2CH2OTs, 2H, t, J=7.3 Hz), 2.43 (OTs, 3H,