Job/Unit: O20918
/KAP1
Date: 17-09-12 10:28:13
Pages: 13
Suzuki–Miyaura Coupling of Heteroaryl Chlorides and Tosylates
[8]
a) L. Ackermann, H. K. Potukuchi, A. Althammer, R. Born,
P. M aye r, Org. Lett. 2010, 12, 1004; b) A. Bermejo, A. Ros, R.
Fernandez, J. M. Lassaletta, J. Am. Chem. Soc. 2008, 130,
15798; c) N. Kataoka, Q. Shelby, J. P. Stambuli, J. F. Hartwig,
J. Org. Chem. 2002, 67, 5553; d) G. Y. Li, Angew. Chem. 2001,
113, 1561; Angew. Chem. Int. Ed. 2001, 40, 1513; e) C. Wolf,
K. Ekoue-Kovi, Eur. J. Org. Chem. 2006, 1917; f) H. Ohta, M.
Tokunaga, Y. Obora, T. Iwai, T. Iwasawa, T. Fujihara, Y. Tsuji,
Org. Lett. 2007, 9, 89; g) A. Zapf, R. Jackstell, F. Rataboul, T.
Riermeier, A. Monsees, C. Fuhrmann, N. Shaikh, U. Dingerd-
issen, M. Beller, Chem. Commun. 2004, 38; h) Q. Dai, W. Gao,
D. Liu, L. M. Kapes, X. Zhang, J. Org. Chem. 2006, 71, 3928.
a) A. F. Littke, G. C. Fu, Angew. Chem. 1998, 110, 3586; An-
gew. Chem. Int. Ed. 1998, 37, 3387; b) D. W. Old, J. P. Wolfe,
S. L. Buchwald, J. Am. Chem. Soc. 1998, 120, 9722; c) C. M.
Zhang, J. K. Huang, M. L. Trudell, S. P. Nolan, J. Org. Chem.
1999, 64, 3804.
a) C. M. So, C. P. Lau, F. Y. Kwong, Angew. Chem. 2008, 120,
8179; Angew. Chem. Int. Ed. 2008, 47, 8059; b) Z.-Y. Tang, Q.-
S. Hu, J. Am. Chem. Soc. 2004, 126, 3058; c) C. M. So, C. P.
Lau, A. S. C. Chan, F. Y. Kwong, J. Org. Chem. 2008, 73, 7731;
d) H. N. Nguyen, X. Huang, S. L. Buchwald, J. Am. Chem.
Soc. 2003, 125, 11818; e) B. Bhayana, B. P. Fors, S. L. Buch-
wald, Org. Lett. 2009, 11, 3954.
a) J. J. Yin, M. P. Rainka, X. X. Zhang, S. L. Buchwald, J. Am.
Chem. Soc. 2002, 124, 1162; b) S. D. Walker, T. E. Barder, J. R.
Martinelli, S. L. Buchwald, Angew. Chem. 2004, 116, 1907; An-
gew. Chem. Int. Ed. 2004, 43, 1871; c) G. Altenhoff, R. God-
dard, C. W. Lehmann, F. Glorius, J. Am. Chem. Soc. 2004, 126,
15195; d) M. G. Organ, S. Çalimsiz, M. Sayah, K. H. Hoi, A. J.
Lough, Angew. Chem. 2009, 121, 2419; Angew. Chem. Int. Ed.
2009, 48, 2383; e) T. Hoshi, T. Nakazawa, I. Saitoh, A. Mori,
T. Suzuki, J.-i. Sakai, H. Hagiwara, Org. Lett. 2008, 10, 2063;
f) W. Tang, A. G. Capacci, X. Wei, W. Li, A. White, N. D. Patel,
J. Savoie, J. J. Gao, S. Rodriguez, B. Qu, N. Haddad, B. Z. Lu,
D. Krishnamurthy, N. K. Yee, C. H. Senanayake, Angew.
Chem. 2010, 122, 6015; Angew. Chem. Int. Ed. 2010, 49, 5879.
sequentially charged with Pd(OAc)2 (18 mg, 0.08 mmol), XPhos
(45.6 mg, 0.1 mmol), 3-chloropyridine (452 mg, 4 mmol), [N-(tert-
butoxycarbonyl)-2-indolyl]boronic acid (1.25 g, 4.8 mmol), n-do-
decane (320 μL, GC internal standard), and degassed n-butanol
(22.4 mL). The mixture was stirred at 25 °C for 15 min, and then
a solution of CsOH·H2O (1.135 g, 6.8 mmol) in degassed H2O
(5.6 mL) was added in one portion to initiate the Suzuki reaction.
The Schlenk flask was sealed with a septum and the reaction mix-
ture was stirred vigorously at 25 °C for 5 min until the 3-chloropyr-
idine had been fully consumed (as monitored by GC). After routine
work-up and purification by flash chromatography (1:50 ethyl acet-
ate/hexane), the product was obtained as a white solid (1.14 g,
97%).
[9]
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures for synthesis of substrates, Suzuki
coupling, mechanistic study and characterization of new com-
pounds.
[10]
Acknowledgments
We thank the Singapore National Research Foundation (NRF-
RF2008-10) and Nanyang Technological University for financial
support, and Johnson Matthey for a gift of palladium. J. Y., S. L.,
and J.-F. Z. contributed equally to experiments in this work.
[11]
[1] For reviews, see: a) N. Miyaura, A. Suzuki, Chem. Rev. 1995,
95, 2457; b) F. Bellina, A. Carpita, R. Rossi, Synthesis 2004,
2419; c) S. Kotha, K. Lahiri, D. Kashinath, Tetrahedron 2002,
58, 9633; d) N. Miyaura, Top. Curr. Chem. 2002, 219, 11; e)
A. Suzuki, J. Organomet. Chem. 1999, 576, 147; f) V. F. Slagt,
A. H. M. de Vries, J. G. de Vries, R. M. Kellogg, Org. Process
Res. Dev. 2009, 14, 30; g) J.-P. Corbet, G. Mignani, Chem. Rev.
2006, 106, 2651.
[2] a) T. Ishiyama, N. Miyaura, J. Organomet. Chem. 2003, 680, 3;
b) J.-Y. Cho, M. K. Tse, D. Holmes, R. E. Maleczka Jr, M. R.
Smith III, Science 2002, 295, 305; c) T. Ishiyama, J. Takagi,
J. F. Hartwig, N. Miyaura, Angew. Chem. 2002, 114, 3182; An-
gew. Chem. Int. Ed. 2002, 41, 3056; d) I. A. I. Mkhalid, J. H.
Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig, Chem.
Rev. 2010, 110, 890.
[3] a) K. L. Billingsley, T. E. Barder, S. L. Buchwald, Angew.
Chem. 2007, 119, 5455; Angew. Chem. Int. Ed. 2007, 46, 5359;
b) M. Murata, T. Oyama, S. Watanabe, Y. Masuda, J. Org.
Chem. 2000, 65, 164; c) T. Ishiyama, N. Miyaura, J. Organomet.
Chem. 2000, 611, 392; d) G. A. Molander, S. L. J. Trice, S. D.
Dreher, J. Am. Chem. Soc. 2010, 132, 17701.
[4] a) S. D. Roughley, A. M. Jordan, J. Med. Chem. 2011, 54, 3451;
b) J. S. Carey, D. Laffan, C. Thomson, M. T. Williams, Org.
Biomol. Chem. 2006, 4, 2337.
[5] a) G. C. Fu, Acc. Chem. Res. 2008, 41, 1555; b) A. Zapf, A.
Ehrentraut, M. Beller, Angew. Chem. 2000, 112, 4315; Angew.
Chem. Int. Ed. 2000, 39, 4153; c) C. A. Fleckenstein, H. Plenio,
Chem. Eur. J. 2007, 13, 2701; d) G. Adjabeng, T. Brenstrum, J.
Wilson, C. Frampton, A. Robertson, J. Hillhouse, J. McNulty,
A. Capretta, Org. Lett. 2003, 5, 953.
[6] a) R. Martin, S. L. Buchwald, Acc. Chem. Res. 2008, 41, 1461;
b) C. M. So, C. P. Lau, F. Y. Kwong, Angew. Chem. 2008, 120,
8179; Angew. Chem. Int. Ed. 2008, 47, 8059.
[7] a) N. Marion, S. P. Nolan, Acc. Chem. Res. 2008, 41, 1440; b)
C. W. K. Gstöttmayr, V. P. W. Böhm, E. Herdtweck, M. Gros-
che, W. A. Herrmann, Angew. Chem. 2002, 114, 1421; Angew.
Chem. Int. Ed. 2002, 41, 1363; c) G. Altenhoff, R. Goddard,
C. W. Lehmann, F. Glorius, Angew. Chem. 2003, 115, 3818;
Angew. Chem. Int. Ed. 2003, 42, 3690; d) M.-T. Chen, D. A.
Vicic, M. L. Turner, O. Navarro, Organometallics 2011, 30,
5052; e) G.-R. Peh, E. A. B. Kantchev, J.-C. Er, J. Y. Ying,
Chem. Eur. J. 2010, 16, 4010.
[12]
[13]
a) K. W. Quasdorf, X. Tian, N. K. Garg, J. Am. Chem. Soc.
2008, 130, 14422; b) B.-T. Guan, Y. Wang, B.-J. Li, D.-G. Yu,
Z.-J. Shi, J. Am. Chem. Soc. 2008, 130, 14468.
a) K. W. Quasdorf, M. Riener, K. V. Petrova, N. K. Garg, J.
Am. Chem. Soc. 2009, 131, 17748; b) K. W. Quasdorf, A. An-
toft-Finch, P. Liu, A. L. Silberstein, A. Komaromi, T. Black-
burn, S. D. Ramgren, K. N. Houk, V. Snieckus, N. K. Garg, J.
Am. Chem. Soc. 2011, 133, 6352; c) A. Antoft-Finch, T. Black-
burn, V. Snieckus, J. Am. Chem. Soc. 2009, 131, 17750; d) L.
Xu, B.-J. Li, Z.-H. Wu, X.-Y. Lu, B.-T. Guan, B.-Q. Wang, K.-
Q. Zhao, Z.-J. Shi, Org. Lett. 2010, 12, 884; e) Review: B. M.
Rosen, K. W. Quasdorf, D. A. Wilson, N. Zhang, A.-M. Re-
smerita, N. K. Garg, V. Percec, Chem. Rev. 2011, 111, 1346.
R. Capdeville, E. Buchdunger, J. Zimmermann, A. Matter, Nat.
Rev. Drug Discovery 2002, 1, 493.
J. Magano, J. R. Dunetz, Chem. Rev. 2011, 111, 2177.
X. Jiang, G. T. Lee, E. B. Villhauer, K. Prasad, M. Prashad,
Org. Process Res. Dev. 2010, 14, 883.
Examples: a) S. C. Goodacre, L. J. Street, D. J. Hallett, J. M.
Crawforth, S. Kelly, A. P. Owens, W. P. Blackaby, R. T. Lewis,
J. Stanley, A. J. Smith, P. Ferris, B. Sohal, S. M. Cook, A. Pike,
N. Brown, K. A. Wafford, G. Marshall, J. L. Castro, J. R. At-
ack, J. Med. Chem. 2005, 49, 35; b) M. G. N. Russell, R. W.
Carling, L. J. Street, D. J. Hallett, S. Goodacre, E. Mezzogori,
M. Reader, S. M. Cook, F. A. Bromidge, R. Newman, A. J.
Smith, K. A. Wafford, G. R. Marshall, D. S. Reynolds, R.
Dias, P. Ferris, J. Stanley, R. Lincoln, S. J. Tye, W. F. A. Shep-
pard, B. Sohal, A. Pike, M. Dominguez, J. R. Atack, J. L. Cas-
tro, J. Med. Chem. 2006, 49, 1235.
[14]
[15]
[16]
[17]
[18]
G. L. Allsop, A. J. Cole, M. E. Giles, E. Merifield, A. J. Noble,
M. A. Pritchett, L. A. Purdie, J. T. Singleton, Org. Process Res.
Dev. 2009, 13, 751.
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