5436
C. Schneider et al. / Tetrahedron 65 (2009) 5427–5437
9633–9695; (e) Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 4176–
4211; (f) Suzuki, A. J. Organomet. Chem. 2002, 653, 83–90; (g) Stanforth, S. P.
Tetrahedron 1998, 54, 263–303; (h) Miyaura, M.; Suzuki, A. Chem. Rev. 1995, 95,
2457–2483; (i) Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20,
3437–3440.
8.8 Hz), 7.60 (d, 2H, J¼8.9 Hz), 7.56 (d, 2H, J¼8.9 Hz), 7.52 (tt, 1H,
J¼1.3 and 6.0 Hz), 7.45–7.39 (m, 2H), 7.02 (d, 2H, J¼8.9 Hz), 7.03 (d,
2H, J¼8.9 Hz), 3.88 (s, 3H), 3.87 (s, 3H); 13C NMR (75 MHz, CDCl3)
d
159.7 (C), 159.3 (C), 150.2 (C), 145.8 (CH), 138.8 (C), 137.1 (2 C),
2. (a) Diebolt, O.; Braunstein, P.; Nolan, S. P.; Cazin, C. S. J. Chem. Commun. 2008,
3190–3192; (b) Zim, D.; Nobre, S. M.; Monteiro, A. L. J. Mol. Catal. A: Chem. 2008,
287, 16–23; (c) Dawood, K. M. Tetrahedron 2007, 63, 9642–9651; (d) Thimmaiah,
M.; Fang, S. Tetrahedron 2007, 63, 6879–6886; (e) Li, J. H.; Zhu, Q. M.; Xie, Y. X.
Tetrahedron 2006, 62, 10888–10895; (f) So, C. M.; Lau, C. P.; Kwong, F. Y. Org.
Lett. 2007, 9, 2795–2798; (g) Cho, S. D.; Kim, H. K.; Yim, H. S.; Kim, M. R.; Lee, J.
K.; Kim, J. J.; Yoon, Y. J. Tetrahedron 2007, 63, 1345–1352; (h) Mai, W.; Lv, G.; Gao,
L. Synlett 2007, 2247–2251; (i) Ohta, H.; Tokunaga, M.; Obora, Y.; Iwai, T.;
Iwasawa, T.; Fujihara, T.; Tsuji, Y. Org. Lett. 2007, 9, 89–92; (j) Dai, Q.; Gao, W.;
Liu, D.; Kapes, L. M.; Zhang, X. J. Org. Chem. 2006, 71, 3928–3934; (k) Acker-
mann, L.; Born, R. Angew. Chem., Int. Ed. 2005, 44, 2444–2447; (l) Liu, D.; Gao,
W.; Dai, Q.; Zhang, X. Org. Lett. 2005, 7, 4907–4910; (m) Zapf, A.; Beller, M.
Chem. Commun. 2005, 431–440; (n) Navarro, O.; Kaur, H.; Mahjoor, P.; Nolan, S.
P. J. Org. Chem. 2004, 69, 3173–3180; (o) Harkal, S.; Rataboul, F.; Zapf, A.;
Fuhrmann, C.; Riermeier, T.; Monsees, A.; Beller, M. Adv. Synth. Catal. 2004, 346,
1742–1748; (p) Navarro, O.; Kelly, R. A.; Nolan, S. P. J. Am. Chem. Soc. 2003, 125,
16194–16195.
3. (a) Bellina, F.; Carpita, A.; Rossi, R. Synthesis 2004, 2419–2440; (b) Christmann,
U.; Vilar, R. Angew. Chem., Int. Ed. 2005, 44, 366–374.
4. (a) Fu, G. C. Acc. Chem. Res. 2008, 41, 1555–1564; (b) Li, J. H.; Deng, C. L.; Xie, Y. X.
Synth. Commun. 2007, 37, 2433–2448; (c) Littke, A. F.; Dai, C.; Fu, G. C. J. Am.
Chem. Soc. 2000, 122, 4020–4028; (d) Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed.
1998, 37, 3387–3388.
5. (a) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461–1473; (b) Bill-
ingsley, K. L.; Barder, T. E.; Buchwald, S. L. Angew. Chem., Int. Ed. 2007, 46, 5359–
5363; (c) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem.
Soc. 2005, 127, 4685–4696; (d) Barder, T. E.; Buchwald, S. L. Org. Lett. 2004, 6,
2649–2652; (e) Walker, S. D.; Barder, T. E.; Martinelli, J. R.; Buchwald, S. L.
Angew. Chem., Int. Ed. 2004, 43, 1871–1876; (f) Wolfe, J. P.; Buchwald, S. L. An-
gew. Chem., Int. Ed. 1999, 38, 2413–2416; (g) Wolfe, J. P.; Singer, R. A.; Yang, B. H.;
Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 9550–9561; (h) Old, D. W.; Wolfe, J. P.;
Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 9722–9723.
134.0 (CH), 133.1 (C), 132.7 (C), 130.3 (C), 129.0 (2 CH), 128.4 (2 CH),
128.3 (2 CH), 127.5 (2 CH),127.4 (CH),126.3 (CH), 123.5 (C), 119.0 (C),
118.6 (CH), 115.3 (CH), 114.7 (2 CH), 114.4 (2 CH), 55.4 (2 CH3); MS
(ESI) m/z 521.0 [MþH]þ, 543.0 [MþNa]þ, 1062.8 [2MþNa]þ; HRMS
(ESI): Calcd for C31H25N2O4S [MþH]þ: 521.1535. Found: 521.1534.
3.11. Typical procedure for Suzuki reactions with two
different boronic acids from 2-chloro or 4-chloro 6-
bromopyrido[2,3-b]indole
At rt and under an inert atmosphere, a solution of Pd(PPh3)4
(22 mg, 0.019 mmol, 0.08 equiv), 4-methoxyphenylboronic acid (4)
(40 mg, 0.261 mmol, 1.1 equiv), and K2CO3 (99 mg, 0.714 mmol,
3 equiv) in H2O (2.5 mL) was added to a solution of 23 or 25
(100 mg, 0.238 mmol) in 1,4-dioxane (10 mL). This solution was
stirred at 70 ꢀC for 4 h. After cooling to rt, (E)-phenylvinylboronic
acid (5) (39 mg, 0.262 mmol, 1.1 equiv) was added to the solution.
This solution was stirred at 100 ꢀC for 2 h. After cooling to rt, the
solution was diluted with H2O and extracted with EtOAc
(3ꢁ20 mL). The combined organic layers were dried over MgSO4,
then filtered through Celite, and the solvents were removed under
reduced pressure. The crude product was purified by flash chro-
matography (CH2Cl2/PE 1:1 or CH2Cl2/PE 7:3) to afford 32 or 34 in
54% or 71% yield.
6. (a) Billingsley, K.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 3358–3366; (b)
Guram, A. S.; Wang, X.; Bunel, E. E.; Faul, M. M.; Larsen, R. D.; Martinelli, M. J.
J. Org. Chem. 2007, 72, 5104–5112; (c) Billingsley, K. L.; Anderson, K. W.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2006, 45, 3484–3488; (d) Guram, A. S.;
King, A. O.; Allen, J. G.; Wang, X.; Schenkel, L. B.; Chan, J.; Bunel, E. E.; Faul, M. M.;
Larsen, R. D.; Martinelli, M. J.; Reider, P. J. Org. Lett. 2006, 8,1787–1789; (e) Kudo, N.;
Perseghini, M.; Fu, G. C. Angew. Chem., Int. Ed. 2006, 45, 1282–1284; (f) Cooke, G.;
Augier de Cremiers, H.; Rotello, V. M.; Tarbit, B.; Vanderstraeten, P. E. Tetrahedron
2001, 57, 2787–2789.
7. (a) Campeau, L. C.; Fagnou, K. Chem. Soc. Rev. 2007, 36, 1058–1068; (b) Kha-
napure, S. P.; Garvey, D. S. Tetrahedron Lett. 2004, 45, 5283–5286; (c) Molander,
G. A.; Yun, C. S. Tetrahedron 2002, 58, 1465–1470; (d) Lohse, O.; Thevenin, P.;
Waldvogel, E. Synlett 1999, 45–48; (e) Cruskie, M. P.; Zoltewicz, J. A., Jr.; Abboud,
K. A. J. Org. Chem. 1995, 60, 7491–7495; (f) Rocca, P.; Marsais, F.; Godard, A.;
Queguiner, G. Tetrahedron 1993, 49, 3325–3342.
3.12. Typical procedure for Suzuki reactions with two
different boronic acids from 6-bromo-3-chloropyrido[2,3-
b]indole
A sealed pressure tube with a stir bar was charged with Pd(OAc)2
(5 mg, 0.02 mmol, 0.08 equiv), S-Phos (17 mg, 0.04 mmol, 0.16 equiv),
6-bromo-3-chloropyrido[2,3-b]indole 24 (100 mg, 0.238 mmol), 4-
methoxyphenylboronic acid (4) (44 mg, 0.286 mmol, 1.2 equiv),
and K3PO4 (151 mg, 0.71 mmol, 3 equiv). The tube was evacuated
and back-filled with argon (this was repeated three additional
times). Freshly degassed 1,4-dioxane (650 mL) was added and the
8. (a) Schirok, H. J. Org. Chem. 2006, 71, 5538–5545; (b) Allegretti, M.; Arcadi, A.;
Marinelli, F.; Nicolini, L. Synlett 2001, 609–612.
reaction mixture was stirred at 50 ꢀC for 5 h. After cooling to rt, (E)-
phenylvinylboronic acid (5) (88 mg, 0.595 mmol, 2.5 equiv) was
added to the solution. This solution was stirred at 100 ꢀC for 12 h.
After cooling to rt, the solution was diluted with H2O and extracted
with EtOAc (3ꢁ20 mL). The combined organic layers were dried
over MgSO4, then filtered through Celite, and the solvents were
removed under reduced pressure. The crude product was purified
by flash chromatography (CH2Cl2/PE 3:1) to afford 33 in 65% yield.
9. (a) Beletskaya, I. P.; Tsvetkov, A. V.; Tsvetkov, P. V.; Latyshev, G. V.; Lukashev, N.
V. Russ. Chem. Bull. 2005, 54, 215–219; (b) Beletskaya, I. P.; Tsvetkov, A. V.;
Latyshev, G. V.; Lukashev, N. V. Russ. J. Org. Chem. 2003, 39, 1660–1667; (c)
Tagata, T.; Nishida, M. J. Org. Chem. 2003, 68, 9412–9415; (d) Tsvetkov, A. V.;
Latyshev, G. V.; Lukashev, N. V.; Beletskaya, I. P. Tetrahedron Lett. 2002, 43,
7267–7270; (e) Ali, N. M.; McKillop, A.; Mitchell, M. B.; Rebelo, R. A.; Wallbank,
P. J. Tetrahedron 1992, 48, 8117–8126.
10. (a) Bracher, F.; Hildebrand, D. Liebigs Ann. Chem. 1992, 1315–1319; (b) Bracher,
F.; Hildebrand, D. Liebigs Ann. Chem. 1993, 1335–1337.
11. (a) Bolton, D.; Forbes, I. T.; Hayward, C. J.; Piper, D. C.; Thomas, D. R.; Thompson,
M.; Upton, N. Bioorg. Med. Chem. Lett. 1993, 3, 1941–1946; (b) Love, B. E. Top.
Heterocycl. Chem. 2006, 2, 93–128; (c) Moquin-Pattey, C.; Guyot, M. Tetrahedron
1989, 45, 3445–3450; (d) Kim, J. S.; Shin-ya, K.; Furihata, K.; Hayakawa, Y.; Seto,
H. Tetrahedron Lett. 1997, 38, 3431–3434.
12. (a) Schneider, C.; Gueyrard, D.; Popowycz, F.; Joseph, B.; Goekjian, P. G. Synlett
2007, 2237–2241; (b) Dininno, F. P.; Guthikonda, R. N.; Meurer, L.C. U.S. Patent
US 5,532,261; Chem. Abstr. 1996, 125, 167688; (c) Wieczorek, J.; Peczynska-
Czoch, W.; Mordarski, M.; Kaczmarek, L.; Nantka-Namirski, P. Arch. Immunol.
Ther. Exp. 1986, 34, 315–321; (d) Stephenson, L.; Warburton, W. K. J. Chem. Soc. C
1970, 1355–1364; (e) Saxena, J. P. Ind. J. Chem. 1966, 4, 148.
Acknowledgements
`
The authors thank the ‘Ministere de la Recherche et de l’En-
´
seignement Superieur’ for a Graduate Fellowship (C.S.). Financial
support from the European Union (Contract Nꢀ LSHB-CT-2004-
503467) is also gratefully acknowledged.
13. (a) Das, S.; Brown, J. W.; Dong, Q.; Gong, X.; Kaldor, S. W.; Liu, Y.; Paraselli, B. R.;
Scorah, N.; Stafford, J. A.; Wallace, M. B. Appl. Int. WO 2007/044779; Chem.
Abstr. 2007, 146, 441771; (b) Sennhenn, P.; Mantoulidis, A.; Treu, M.; Tontsch-
Grunt, U.; Spevak, W.; McConnell, D.; Schoop, A.; Brueckner, R.; Jacobi, A.;
Guertler, U.; Schnapp, G.; Klein, C.; Himmelsbach, F.; Pautsch, A.; Betzemeier, B.;
Herfurth, L.; Mack, J.; Wiedenmayer, D.; Bader, G.; Reiser, U. Appl. Int. WO 2006/
131552; Chem. Abstr. 2006, 146, 62695; (c) Brown, J. W.; Dong, Q.; Paraselli, B.
R.; Stafford, J. A.; Wallace, M. B.; Wijesekera, H. Appl. Int. WO 2008/054956;
Chem. Abstr. 2008, 148, 495928.
Supplementary data
Supplementary data associated with this article can be found in
References and notes
14. (a) Vera-Luque, P.; Alajarin, R.; Alvarez-Builla, J.; Vaquero, J. J. Org. Lett. 2006, 8,
415–418; (b) Katritzky, A. R.; Lan, X.; Yang, J. Z.; Denisko, O. V. Chem. Rev. 1998,
98, 409–548; (c) Mehta, L. K.; Parrick, J.; Payne, F. J. Chem. Soc., Perkin Trans. 1
1. (a) Corbet, J. P.; Mignani, G. Chem. Rev. 2006, 10, 2651–2710; (b) Yin, L.;
Liebscher, J. Chem. Rev. 2007, 107, 133–173; (c) Miyaura, N. Top. Curr. Chem.
2002, 219, 11–59; (d) Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002, 58,