ORGANIC
LETTERS
2
006
Vol. 8, No. 9
787-1789
New Air-Stable Catalysts for General
and Efficient Suzuki Miyaura
1
−
Cross-Coupling Reactions of Heteroaryl
Chlorides
Anil S. Guram,* Anthony O. King, John G. Allen, Xianghong Wang,
Laurie B. Schenkel, Johann Chan, Emilio E. Bunel, Margaret M. Faul,
Robert D. Larsen, Michael J. Martinelli, and Paul J. Reider
Chemistry Research and DiscoVery, Amgen Inc., One Amgen Center DriVe,
Thousand Oaks, California 91320
Received January 31, 2006
ABSTRACT
New air-stable PdCl
cross-coupling reactions of aryl halides including five-membered heteroaryl halides and heteroatom-substituted six-membered heteroaryl chlorides
{PtBu
(p-R-Ph)} (R ) H, NMe , CF ,) complexes represent simple, general, and efficient catalysts for the Suzuki−Miyaura
2 2 2 2 3
with a diverse range of arylboronic acids. High product yields (89−99% isolated yields) and turn-over-numbers (10 000 TON) are observed.
The Suzuki-Miyaura cross-coupling reaction has emerged
Although catalysts for cross-coupling reactions of aryl
chlorides with a range of electronic and steric properties are
now extensively developed, catalysts for general cross-
coupling reactions of heteroaryl halides, and particularly five-
as one of the most powerful, attractive, and widely utilized
1
methods for the construction of carbon-carbon bonds.
Notably, the pioneering development of novel and highly
2
3
efficient Pd/L catalysts from the groups of Buchwald, Fu,
4
5
6
7
8
9
(5) (a) Zapf, A.; Jackstell, R.; Rataboul, F.; Reirmeier, T.; Monsees, A.;
Fuhrmann, C.; Shaikh, N.; Dingerdissen, U.; Beller, M. Chem. Commun.
Hartwig, Beller, Guram/Bei, Bedford, Li, Herrmann,
1
0
11
Nolan, and Colacot has significantly extended the scope
of the reaction to include aryl chlorides as coupling partners.
2
004, 38-39. (b) Harkal, S.; Ratabul, F.; Zapf, A.; Fuhrmann, C.; Riermeier,
T.; Monsees, A.; Beller, M. AdV. Synth. Catal. 2004, 346, 1742-1748. (c)
Zapf, A.; Ehrentraut, A.; Beller, M. Angew. Chem., Int. Ed. 2000, 39, 4153-
4
155.
(
1) Selected recent reviews: (a) Miyaura, N. Top. Curr. Chem. 2002,
(6) (a) Bei, X.; Turner, H. W.; Weinberg, W. H.; Guram, A. S. J. Org.
2
5
2
19, 11-59. (b) Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002,
8, 9633-9695. (c) Bellina, F.; Carpita, A.; Rossi, R. Synthesis 2004, 15,
419-2440. (d) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire,
Chem. 1999, 64, 6797-6803. (b) Bei, X.; Crevier, T.; Guram, A. S.;
Jandeleit, B.; Powers, T. S.; Turner, H. W.; Uno, T.; Weinberg, W. H.
Tetrahedron Lett. 1999, 40, 3855-3858.
M. Chem. ReV. 2002, 102, 1359-1470. (e) Littke, A. F.; Fu, G. C. Angew.
Chem., Int. Ed. 2002, 41, 4176-4211.
(7) (a) Bedford, R. B.; Cazin, C. S. J.; Hzelwood, S. L. Angew. Chem.,
Int. Ed. 2002, 41, 4120-4122. (b) Bedford, R. B.; Cazin, C. S. J. Chem.
Commun. 2001, 1540-1541.
(2) (a) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J.
Am. Chem. Soc. 2005, 127, 4685-4696. (b) Walker, S. D.; Barder, T. E.;
(8) Li, G. Y.; Zheng, G.; Noonan, A. F. J. Org. Chem. 2001, 66, 8677-
Martinelli, J. R.; Buchwald, S. L. Angew. Chem., Int. Ed. 2004, 43, 1871-
8678.
1
876. (c) Yin, J.; Rainka, M. P.; Zhang, X.-X; Buchwald, S. L. J. Am.
(9) Gstottmayr, C. W. K.; Bohm, V. P. W.; Herdtweck, E.;
Grosche, M.; Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1363-
1365.
Chem. Soc. 2002, 124, 1162-1163.
(3) (a) Kirshhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem., Int. Ed. 2002,
4
2
1, 1945-1947. (b) Liu, S.-Y.; Choi, M. J.; Fu, G. C. Chem. Commun.
(10) (a) Navarro, O.; Kaur, H.; Mahjoor, P.; Nolan, S. P. J. Org. Chem.
2004, 69, 3173-3180. (b) Navarro, O.; Kelly, R. A., III; Nolan, S. P. J.
Am. Chem. Soc. 2003, 125, 16194-16195.
001, 2408-2409.
(4) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F. J. Org. Chem.
2
002, 67, 5553-5566.
(11) Colacot, T. J.; Shea, H. A. Org. Lett. 2004, 6, 3731-3734.
1
0.1021/ol060268g CCC: $33.50
© 2006 American Chemical Society
Published on Web 04/01/2006