ORGANIC
LETTERS
2009
Vol. 11, No. 2
453-456
FeCl3-Catalyzed 1,2-Addition Reactions
of Aryl Aldehydes with Arylboronic
Acids
Tao Zou,† Sha-Sha Pi,† and Jin-Heng Li*,†,‡
College of Chemistry and Materials Science, Wenzhou UniVersity, Wenzhou 325035,
China, and Key Laboratory of Chemical Biology & Traditional Chinese Medicine
Research, Hunan Normal UniVersity, Changsha 410081, China
Received November 6, 2008
ABSTRACT
A novel protocol for the 1,2-addition reactions of electron-deficient aryl aldehydes with arylboronic acids using an inexpensive and environmentally
benign iron catalyst is reported. In the presence of FeCl3 and 2-(di-tert-butylphosphino)biphenyl, 1,2-addition reactions of various electron-
deficient aryl aldehydes with arylboronic acids provided the corresponding biaryl methanols in moderate to excellent yields.
Rhodium-catalyzed 1,2-addition of aldehydes with orga-
noboronic acids was first reported by Miyaura in 1998.
Shortly after, other transition-metal-catalyzed versions of
this transformation emerged, and the method quickly
became a valuable tool for carbon-carbon bond forma-
tion.1-6 However, these transformations are often used
highly expensive transition metal catalysts, such as rhodi-
um,1,2 palladium,3 platinum,4 and nickel5 complexes. Only
one paper has reported on the use of inexpensive copper
catalyst.6 In view of both economy and environment, a great
challenge still remains regarding the use of some inexpensive
and environmentally benign catalysts for the 1,2-addition
reaction. Recently, iron, an inexpensive and environmentally
benign catalyst, has been proven to be efficient for the
formation of carbon-carbon and carbon-heteroatom bonds.7
A representative example is that iron displayed highly
† Wenzhou University.
‡ Hunan Normal University.
(1) For reviews, see: (a) Li, C.-J. Acc. Chem. Res. 2002, 35, 533. (b)
Fagnou, K.; Lautens, M. Chem. ReV. 2003, 103, 169. (c) Hayashi, T.;
(3) (a) Yamamoto, T.; Ohta, T.; Ito, Y. Org. Lett. 2005, 7, 4153. (b)
Suzuki, K.; Arao, T.; Ishii, S.; Maeda, Y.; Kondo, K.; Aoyama, T.
Tetrahedron 2006, 47, 5789. (c) He, P.; Lu, Y.; Dong, C.-G.; Hu, Q.-S.
Org. Lett. 2007, 9, 343. (d) Lin, S.; Lu, X. J. Org. Chem. 2007, 72, 9757.
(e) Qin, C.; Wu, H.; Cheng, J.; Chen, X.; Liu, M.; Zhang, W.; Su, W.;
Ding, J. J. Org. Chem. 2007, 72, 4102. (f) Qin, C.; Chen, J.; Wu, H.; Cheng,
J.; Zhang, Q.; Zou, B.; Su, W.; Ding, J. Tetrahedron Lett. 2008, 49, 1884.
(g) Qin, C.; Wu, H.; Chen, J.; Liu, M.; Cheng, J.; Su, W.; Ding, J. Org.
Lett. 2008, 10, 1537. (h) Kuriyama, M.; Shimazawa, R.; Shirai, R. J. Org.
Chem. 2008, 73, 1597. (i) Kuriyama, M.; Shimazawa, R.; Enomoto, T.;
Shirai, R. J. Org. Chem. 2008, 73, 6939.
Yamasaki, K. Chem. ReV. 2003, 103, 2829
.
(2) For selected papers, see: (a) Sakai, M.; Ueda, M.; Miyaura, N. Angew.
Chem., Int. Ed. 1998, 37, 3279. (b) Ueda, M.; Miyaura, N. J. Org. Chem.
2000, 65, 4450. (c) Pourbaix, C.; Carreaux, F.; Carboni, B. Org. Lett. 2001,
3, 803. (d) Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am.
Chem. Soc. 2002, 124, 5052. (e) Krug, C.; Hartwig, J. F. J. Am. Chem.
Soc. 2002, 124, 1674. (f) Pucheault, M.; Darses, S.; Genet, J.-P. J. Am.
Chem. Soc. 2004, 126, 15356. (g) Son, S. U.; Kim, S. B.; Reingold, J. A.;
Carpenter, G. B.; Sweigart, D. A. J. Am. Chem. Soc. 2005, 127, 12238. (h)
Duan, H.-F.; Xie, J.-H.; Shi, W.-J.; Zhang, Q.; Zhou, Q.-L. Org. Lett. 2006,
8, 1479. (i) Suzuki, K.; Ishii, S.; Kondo, K.; Aoyama, T. Synlett 2006,
648. (j) Suzuki, K.; Kondo, K.; Aoyama, T. Synthesis 2006, 1360. (k) Jagt,
R. B. C.; Toullec, P. Y.; Schudde, E. P.; De Vries, J. G.; Feringa, B. L.;
Minnaard, A. J. J. Comb. Chem. 2007, 9, 407. (l) Noe¨l, T.; Vandyck, K.;
Van der Eycken, J. Tetrahedron 2007, 63, 12961. (m) Gois, P. M.; Trindade,
A. F.; Veiros, L. F.; Andre´, V.; Duarte, M. T.; Afonso, C. A. M.; Caddick,
(4) Liao, Y.-X.; Xing, C.-H.; He, P.; Hu, Q.-S. Org. Lett. 2008, 10,
2509.
(5) (a) Takahashi, G.; Shirakawa, E.; Tsuchimoto, T.; Kawakami, Y.
Chem. Commun. 2005, 1459. (b) Arao, T.; Kondo, K.; Aoyama, T.
Tetrahedron Lett. 2007, 48, 4115. (c) Arao, T.; Kondo, K.; Aoyama, T.
Tetrahedron 2007, 63, 5261.
S.; Cloke, F. G. N. Angew. Chem., Int. Ed. 2007, 46, 5750
.
(6) Tomita, D.; Kanai, M.; Shibasaki, M. Chem. Asian J. 2006, 1, 161.
10.1021/ol802529p CCC: $40.75
Published on Web 12/15/2008
2009 American Chemical Society