8554
D. Gauthier et al. / Tetrahedron 65 (2009) 8542–8555
1361, 1207, 1126, 1035, 881, 674; HRMS (ESþ) m/z [MþH]þ calcd for
Rh2(NHCOCF3)4 (13 mg, 0.02 mmol, 5 mol %), distilled Et3N (171
mL,
C31H47N2O4Si: 539.3305; found: 539.3298.
2.50 mmol, 6.25 equiv), and TIPSOTf (135 L, 0.50 mmol,1.25 equiv).
m
Flash column chromatography on silica gel (CH2Cl2/Et2O/Et3N, 5.9/
4.12.2. N,N-Diethyl-1-N-(2,4-dimethoxybenzyl)-6-methoxy-2-(triiso-
propylsilyloxy)-1H-indole-3-carboxamide (16j). Compound 16j was
prepared according to the general procedure (E) reported for 16a
starting from diazo 15j (176 mg, 0.40 mmol, 1 equiv),
4/0.1) afforded 16m (102 mg, 42%) as a light yellow oil. 1H NMR
(300 MHz, CDCl3)
d
7.40–7.37 (m, 2H), 7.27 (dd, J¼7.8, 1.4 Hz, 1H),
6.50 (d, J¼8.5 Hz, 1H), 6.46 (d, J¼2.3 Hz, 1H), 6.26 (dd, J¼8.5, 2.3 Hz,
1H), 5.19 (s, 2H), 3.88 (s, 3H), 3.73 (s, 3H), 3.48 (q, J¼7.1 Hz, 4H), 1.37
(hep, J¼7.5 Hz, 3H), 1.15 (t, J¼7.1 Hz, 6H), 1.04 (d, J¼7.5 Hz, 18H); 13C
Rh2(NHCOCF3)4 (13 mg, 0.02 mmol, 5 mol %), distilled Et3N (171
mL,
2.50 mmol, 6.25 equiv), and TIPSOTf (135 L, 0.50 mmol,
m
NMR (75 MHz, CDCl3) d 166.0, 160.6, 157.6, 148.5, 130.0, 128.1, 127.9,
1.25 equiv). Flash column chromatography on silica gel (CH2Cl2/
Et2O/Et3N, 5.9/4/0.1) afforded 16j (200 mg, 88%) as a light yellow oil.
124.1 (q, J¼251.3 Hz), 122.4 (q, J¼31.8 Hz), 118.4, 117.35, 117.33 (q,
J¼3.0 Hz), 106.9 (d, J¼4.4 Hz), 104.4, 98.5, 94.0, 55.6, 55.5, 48.9, 41.3
(2C), 18.1 (6C), 14.1 (2C), 13.7 (2C), 12.5 (3C); 19F NMR (282 MHz,
1H NMR (300 MHz, CDCl3)
d
7.27 (d, J¼8.5 Hz, 1H), 6.75 (dd, J¼8.5,
2.3 Hz, 1H), 6.64 (d, J¼2.3 Hz, 1H), 6.53 (d, J¼8.5 Hz, 1H), 6.49 (d,
J¼2.4 Hz, 1H), 6.29 (dd, J¼8.5, 2.4 Hz, 1H), 5.15 (s, 2H), 3.90 (s, 3H),
3.76 (s, 6H), 3.53 (q, J¼7.0 Hz, 4H), 1.38 (hep, J¼7.5 Hz, 3H), 1.19 (t,
J¼7.0 Hz, 6H), 1.07 (d, J¼7.5 Hz, 18H); 13C NMR (75 MHz, CDCl3)
CDCl3)
d
ꢁ60.3; IR (neat, cmꢁ1) 3424, 2940, 2864, 1614, 1557, 1462,
1301, 1208, 1158, 1112, 881; HRMS (ESþ) m/z [MþNa]þ calcd for
C32H45F3N2O4Si Na: 629.2998; found: 629.3019.
d
166.8, 160.2, 157.5, 155.4, 145.8, 131.7, 127.8, 119.6, 119.1, 117.9,
Acknowledgements
109.0, 104.2, 98.3, 94.4, 92.8, 55.8, 55.5, 55.4, 41.5(2C), 39.7, 18.2
(6C), 14.1 (2C), 13.6 (3C); IR (neat, cmꢁ1) 3424, 2938, 2863, 1713,
1614, 1455, 1377, 1260, 1207, 1035, 809; HRMS (ESþ) m/z [MþNa]þ
calcd for C32H48N2O5SiNa: 591.3230; found: 591.3249.
We thank the Institut de Chimie des Substances Naturelles for
a fellowship (D.G.).
References and notes
4.12.3. N,N-Diethyl-6-(tert-butyldiphenylsilyloxy)-1-N-(2,4-dime-
thoxybenzyl)-2-(triisopropylsilyloxy)-1H-indole-3-carboxamide
(16k). Compound 16k was prepared according to the general
procedure (E) reported for 16a starting from diazo 15k (266 mg,
0.40 mmol, 1 equiv), Rh2(NHCOCF3)4 (13 mg, 0.02 mmol, 5 mol %),
1. (a) Sundberg, R. J. The Chemistry of Indoles; Academic: New York, NY, 1970; (b)
Sundberg, R. J. Indoles; Academic: London, 1996.
2. (a) Bindra, J. S. In The Alkaloids; Manske, R. H. F., Ed.; Academic: New York, NY,
1973; Vol. 14, pp 84–121; (b) Marti, C.; Carreira, E. M. Eur. J. Org. Chem. 2003,
2209–2219; (c) Galliford, C. V.; Scheidt, K. A. Angew. Chem., Int. Ed. 2007, 46,
8748–8758.
distilled Et3N (171 mL, 2.50 mmol, 6.25 equiv), and TIPSOTf (135 mL,
0.50 mmol, 1.25 equiv). Flash column chromatography on silica gel
´
3. Jossang, A.; Jossang, P.; Hadi, H. A.; Sevenet, T.; Bodo, B. J. Org. Chem. 1991, 56,
6527–6530.
(CH2Cl2/Et2O/heptane/Et3N, 4.9/3/2/0.1) afforded 16k (289 mg,
4. Cui, C. B.; Kakeya, H.; Osada, H. J. Antibiot. 1996, 49, 832–835.
5. Stratmann, K.; Moore, R. E.; Bonjouklian, R.; Deeter, J. B.; Patterson, G. M. L.;
Shaffer, S.; Smith, C. D.; Smitka, T. A. J. Am. Chem. Soc. 1994, 116, 9935–9942.
6. Gallagher, G.; Lavanchy, P. G.; Wilson, J. W.; Hieble, J. P.; DeMarinis, R. M. J. Med.
Chem. 1985, 28, 1533–1536.
91%) as a light yellow oil. 1H NMR (300 MHz, CDCl3)
d 7.62 (dd,
J¼7.9, 1.1 Hz, 4H), 7.35–7.22 (m, 6H), 7.01 (d, J¼8.5 Hz, 1H), 6.54 (dd,
J¼8.5, 2.1 Hz, 1H), 6.42 (d, J¼2.1 Hz, 1H), 6.37 (d, J¼2.3 Hz, 1H), 6.32
(d, J¼8.5 Hz, 1H), 6.15 (dd, J¼8.5, 2.3 Hz, 1H), 4.88 (s, 2H), 3.74 (s,
3H), 3.73 (s, 3H), 3.45 (q, J¼7.0 Hz, 4H), 1.32–1.22 (m, 3H), 1.13–1.07
(m, 6H), 1.03 (br s, 9H), 0.99 (d, J¼7.5 Hz, 18H); 13C NMR (75 MHz,
7. Drugs Future 1990, 15, 898–901.
8. Mendel, D. B.; Laird, A. D.; Xin, X.; Louie, S. G.; Christensen, J. G.; Li, G.; Schreck,
R. E.; Abrams, T. J.; Ngai, T. J.; Lee, L. B.; Murray, L. J.; Carver, J.; Chan, E.; Moss, K.
G.; Haznedar, J. O.; Sukbuntherng, J.; Blake, R. A.; Sun, L.; Tang, C.; Miller, T.;
Shirazian, S.; McMahon, G.; Cherrington, J. M. Clin. Cancer Res. 2003, 9, 327–337.
9. For selected examples, see: (a) Edmondson, S.; Danishefsky, S. J.; Sepp-Lor-
enzino, L.; Rosen, N. J. Am. Chem. Soc. 1999, 121, 2147–2155; (b) Tratrat, C.;
CDCl3) d 166.9, 160.0, 157.3, 150.7, 146.0, 135.8 (4C), 133.7 (2C), 131.6,
129.8 (2C), 127.7 (5C), 119.8, 118.7, 117.9, 113.7, 104.0, 100.6, 98.3,
92.7, 55.5, 55.3, 41.3 (2C), 39.7, 26.9 (3C), 18.2, 18.1 (6C), 17.9 (2C),
14.0 (2C), 13.6 (3C), 12.5; IR (neat, cmꢁ1) 3379, 2932, 2863, 1619,
1483, 1462, 1261, 1207, 1105, 1036, 954, 821; HRMS (ESþ) m/z
[MþNa]þ calcd for C47H64N2O5Si2Na: 815.4252; found: 815.4264.
´
Giorgi-Renault, S.; Husson, H.-P. J. Org. Chem. 2000, 65, 6773–6776; (c) Suarez-
Castillo, O. R.; Sa´nchez-Zavala, M.; Mele´ndez-Rodrı´guez, M.; Castela´n-Duarte,
L. E.; Morales-Rı´os, M. S.; Joseph-Nathan, P. Tetrahedron 2006, 62, 3040–3051;
(d) Poriel, C.; Lachia, M.; Wilson, C.; Davies, J. R.; Moody, C. J. J. Org. Chem. 2007,
72, 2978–2987; (e) Artman, G. D., III; Grubbs, A. W.; Williams, R. M. J. Am. Chem.
Soc. 2007, 129, 6336–6342.
10. For selected recent examples, see: (a) Luppi, G.; Cozzi, P. G.; Monari, M.; Kap-
tein, B.; Broxterman, Q. B.; Tomasini, C. J. Org. Chem. 2005, 70, 7418–7421; (b)
Shintani, R.; Inoue, M.; Hayashi, T. Angew. Chem., Int. Ed. 2006, 45, 3353–3356;
(c) Schulz, V.; Davoust, M.; Lemarie´, M.; Lohier, J.-F.; Sopkova de Oliveira Santos,
4.12.4. N,N-Diethyl-1-N-(2,4-dimethoxybenzyl)-6-fluoro-2-(triisopro-
pylsilyloxy)-1H-indole-3-carboxamide (16l). Compound 16l was
prepared according to the general procedure (E) reported for 16a
starting from diazo 15l (171 mg, 0.40 mmol, 1 equiv),
`
J.; Metzner, P.; Briere, J.-F. Org. Lett. 2007, 9, 1745–1749; (d) Malkov, A. V.; Ka-
beshov, M. A.; Bella, M.; Kysilka, O.; Malyshev, D. A.; Pluha´ckova´, K.; Kocovsky, P.
Org. Lett. 2007, 9, 5473–5476; (e) Guo, X.; Huang, H.; Yang, L.; Hu, W. Org. Lett.
2007, 7, 4721–4723.
Rh2(NHCOCF3)4 (13 mg, 0.02 mmol, 5 mol %), distilled Et3N (171
mL,
2.50 mmol, 6.25 equiv), and TIPSOTf (135 L, 0.50 mmol,1.25 equiv).
m
Flash column chromatography on silica gel (CH2Cl2/Et2O/heptane/
11. (a) Jones, K.; Wilkinson, J. J. Chem. Soc., Chem. Commun. 1992, 1767–1769; (b)
Lizos, D.; Tripoli, R.; Murphy, J. A. Chem. Commun. 2001, 2732–2733.
12. Gassman, P. G.; van Bergen, T. J. J. Am. Chem. Soc. 1974, 96, 5508–5512.
13. (a) Wolfe, J. P.; Rennels, R. A.; Buchwald, S. L. Tetrahedron 1996, 52, 7525–7546;
(b) Poondra, R. R.; Turner, N. J. Org. Lett. 2005, 7, 863–866; (c) van den Hoo-
genband, A.; Lange, J. H. M.; den Hartog, J. A. J.; Henzen, R.; Terpstra, J. W.
Tetrahedron Lett. 2007, 48, 4461–4465.
14. (a) Shaughnessy, K. H.; Hamann, B. C.; Hartwig, J. F. J. Org. Chem. 1998, 63, 6546–
6553; (b) Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402–3415; (c) Trost, B. M.;
Frederiksen, M. U. Angew. Chem., Int. Ed. 2005, 44, 308–310; (d) Ku¨ ndig, E. P.;
Seidel, T. M.; Jia, Y.-X.; Bernardinelli, G. Angew. Chem., Int. Ed. 2007, 46, 8484–
8487; (e) Marsden, S. P.; Watson, E. L.; Raw, S. A. Org. Lett. 2008, 10, 2905–2908.
15. (a) Mori, M.; Ban, Y. Tetrahedron Lett. 1976, 17, 1807–1810; (b) Abelman, M. M.;
Oh, T.; Overman, L. E. J. Org. Chem. 1987, 52, 4130–4133; (c) Overman, L. E.;
Rosen, M. D. Angew. Chem., Int. Ed. 2000, 39, 4596–4599; (d) McDermott, M. C.;
Stephenson, G. R.; Walkington, A. J. Synlett 2007, 51–54; (e) Pinto, A.; Jia, X.;
Neuville, L.; Zhu, J. Chem.dEur. J. 2007, 13, 961–967; (f) Ruck, R. T.; Huffman, M.
A.; Kim, M. M.; Shevlin, M.; Kandur, W. V.; Davies, I. W. Angew. Chem., Int. Ed.
2008, 47, 4711–4714.
Et3N, 4.9/3/2/0.1) afforded 16l (160 mg, 72%) as a light yellow oil. 1H
NMR (300 MHz, CDCl3)
d 7.35–7.24 (m, 1H), 6.82–6.76 (m, 1H), 6.74
(dd, J¼9.4, 2.4 Hz, 1H), 6.47 (d, J¼8.4 Hz, 1H), 6.45 (d, J¼2.4 Hz, 1H),
6.25 (dd, J¼8.4, 2.4 Hz,1H), 5.10 (s, 2H), 3.86 (s, 3H), 3.73 (s, 3H), 3.45
(q, J¼7.3 Hz, 4H), 1.32 (hep, J¼7.7 Hz, 3H), 1.15 (m, 6H), 1.03 (d,
J¼7.7 Hz, 18H); 13C NMR (75 MHz, CDCl3)
d 166.5, 160.4, 159.3 (d,
J¼250.1 Hz), 155.6 (2C), 135.5 (d, J¼9.7 Hz), 127.2, 121.7, 119.1 (d,
J¼9.3 Hz), 117.3, 108.4 (d, J¼24.2 Hz), 104.2, 98.5 (2C), 96.5 (d,
J¼26.3 Hz), 55.6 (2C), 41.1 (2C), 40.0, 18.1 (6C), 15.0 (2C), 14.6 (3C);
19F NMR (282 MHz, CDCl3)
d
ꢁ122.4; HRMS (ESþ) m/z [MþNa]þ
calcd for C31H45FN2O4SiNa: 556.3133; found: 556.3139.
4.12.5. N,N-Diethyl-1-N-(2,4-dimethoxybenzyl)-6-(trifluoromethyl)-
2-(triisopropylsilyloxy)-1H-indole-3-carboxamide (16m). Compound
16m was prepared according to the general procedure (E) reported
for 16a starting from diazo 15m (191 mg, 0.40 mmol, 1 equiv),
16. (a) Yanada, R.; Obika, S.; Oyama, M.; Takemoto, Y. Org. Lett. 2004, 6, 2825–2828;
(b) Cheung, W. S.; Patch, R. J.; Player, M. R. J. Org. Chem. 2005, 70, 3741–3744; (c)
Yanada, R.; Obika, S.; Inokuma, T.; Yanada, K.; Yamashita, M.; Ohta, S.;