types of active catalysts have been developed, such as rhodium,4,5
palladium,6 nickel,7 copper,8 and platinum9 complexes.
Palladium-Catalyzed 1,2-Addition of Potassium
Aryl- and Alkenyltrifluoroborates to Aldehydes
using Thioether-Imidazolinium Carbene Ligands
Recently, potassium organotrifluoroborates have been focused
as alternatives to organoboronic acids because of their superior
features.10 Boronic acids often dimerize and trimerize to form
boronic acids anhydrides and boroxines,11 which make difficul-
ties in the direct purification and in the determination of the
exact stoichiometry for reactions. On the other hand, potassium
trifluoroborate salts are quite highly air- and moisture-stable12
crystalline solids that are more easily prepared, purified, and
handled.10 In spite of the advantages, examples of transition-
metal-catalyzed 1,2-addition of potassium organotrifluoroborates
toaldehydesarescarce,andonlytwotypesofrhodium(I)-phosphine
complexes as catalysts for this reaction were reported.10d,13
Herein, we would like to describe the palladium-catalyzed 1,2-
addition of potassium aryl-, heteroaryl-, and alkenyltrifluorobo-
Masami Kuriyama,* Rumiko Shimazawa,
Terumichi Enomoto, and Ryuichi Shirai*
Faculty of Pharmaceutical Sciences, Doshisha Women’s
College of Liberal Arts, Kodo, Kyotanabe,
Kyoto 610-0395, Japan
mkuriyam@dwc.doshisha.ac.jp; rshirai@dwc.doshisha.ac.jp
ReceiVed June 22, 2008
(4) Reviews: (a) Fagnou, K.; Lautens, M. Chem. ReV. 2003, 103, 169–196.
(b) Hayashi, T.; Yamasaki, K. Chem. ReV. 2003, 103, 2829–2844.
¨
(5) Recent examples: (a) Ozdemir, I.; Demir, S.; C¸ etinkaya, B. J. Mol. Catal.
A: Chem. 2004, 215, 45–48. (b) Imlinger, N.; Mayr, M.; Wang, D.; Wurst, K.;
Buchmeiser, M. R. AdV. Synth. Catal. 2004, 346, 1836–1843. (c) Focken, T.;
¨
Rudolph, J.; Bolm, C. Synthesis 2005, 429–436. (d) Ozdemir, I.; Gu¨rbu¨z, N.;
Sec¸kin, T.; C¸ etinkaya, B. Appl. Organomet. Chem. 2005, 19, 633–638. (e) Zang,
¨
W.; Qin, Y.; Zhang, S.; Luo, M. ARKIVOC 2005, 39–48. (f) Ozdemir, I.; Gu¨rbu¨z,
N.; Go¨k, Y.; C¸ etinkaya, B.; C¸ etinkaya, E. Transition Metal Chem. 2005, 30,
367–671. (g) Son, S. U.; Kim, S. B.; Reingold, J. A.; Carpenter, G. B.; Sweigart,
D. A. J. Am. Chem. Soc. 2005, 127, 12238–12239. (h) Huang, R.; Shaughnessy,
¨
K. H. Chem. Commun. 2005, 4484–4486. (i) Yigit, M.; Ozdemir, I.; C¸ etinkaya,
E.; C¸ etinkaya, B. Heteroatom Chem. 2005, 16, 461–465. (j) Imlinger, N.; Wurst,
¨
K.; Buchmeiser, M. R. J. Organomet. Chem. 2005, 690, 4433–4440. (k) Ozdemir,
I.; Demir, S.; C¸ etinkaya, B.; C¸ etinkaya, E. J. Organomet. Chem. 2005, 690,
5849–5855. (l) Chen, J.; Zhang, X.; Feng, Q.; Luo, M. J. Organomet. Chem.
2006, 691, 470–474. (m) Jagt, R. B. C.; Toullec, P. Y.; De Vries, J. G.; Feringa,
B. L.; Minnaard, A. J. Org. Biomol. Chem. 2006, 4, 773–775. (n) Duan, H.-F.;
Xie, J.-H.; Shi, W.-J.; Zhang, Q.; Zhou, Q.-L. Org. Lett. 2006, 8, 1479–1481.
(o) Suzuki, K.; Ishii, S.; Kondo, K.; Aoyama, T. Synlett 2006, 648–650. (p)
Suzuki, K.; Kondo, K.; Aoyama, T. Synthesis 2006, 1360–1364. (q) Yan, C.;
Zeng, X.; Zhang, W.; Luo, M. J. Organomet. Chem. 2006, 691, 3391–3396. (r)
Palladium-catalyzed 1,2-addition of potassium aryl- and
alkenyltrifluoroboratestoaldehydesusingthioether-imidazolinium
carbene ligands proceeded readily under aqueous conditions.
This process tolerated a diverse range of potassium trifluo-
roborate salts and aldehydes, giving a variety of carbinol
derivatives with good to excellent yields.
¨
Ozdemir, I.; Yigit, M.; C¸ etinkaya, E.; C¸ etinkaya, B. Heterocycles 2006, 68, 1371–
1379. (s) Arao, T.; Suzuki, K.; Kondo, K.; Aoyama, T. Synthesis 2006, 3809–
¨
3814. (t) Rafet, K.; Yigit, M.; Ozdemir, I.; C¸ etinkaya, E.; C¸ etinkaya, B.
J. Heterocycl. Chem. 2007, 44, 69–73. (u) Jagt, R. B. C.; Toullec, P. Y.; Schudde,
E. B.; De Vries, J. G.; Feringa, B. L.; Minnaard, A. J. J. Comb. Chem. 2007, 9,
407–414. (v) Gois, P. M. P.; Trindade, A. F.; Veiros, L. F.; Andre´, V.; Duarte,
M. T.; Afonso, C. A. M.; Caddick, S.; Cloke, F. G. N. Angew. Chem., Int. Ed.
2007, 46, 5750–5753. (w) Noe¨l, T.; Vandyck, K.; Van der Eycken, J. Tetrahedron
2007, 63, 12961–12967.
Organoboron compounds are known as useful reagents for
carbon-carbon bond formation with various electrophiles in
the presence of transition metals.1 Particularly, because of the
usefulness of organoboronic acids such as low toxicity and easy
manipulation1 and the importance of the addition products as
intermediates for the synthesis of biologically active com-
pounds,2 transition-metal-catalyzed 1,2-addition reactions of
organoboronic acids to aldehydes have been attracting much
attention since Miyaura and co-workers reported the rhodium-
catalyzed 1,2-addition in 1998.3 For this kind of reaction, several
(6) (a) Yamamoto, T.; Ohta, T.; Ito, Y. Org. Lett. 2005, 7, 4153–4155. (b)
Suzuki, K.; Arao, T.; Ishii, S.; Maeda, Y.; Kondo, K.; Aoyama, T. Tetrahedron
Lett. 2006, 47, 5789–5792. (c) He, P.; Lu, Y.; Dong, C.-G.; Hu, Q.-S. Org. Lett.
2007, 9, 343–346. (d) Qin, C.; Wu, H.; Cheng, J.; Chen, X.; Liu, M.; Zhang,
W.; Su, W.; Ding, J. J. Org. Chem. 2007, 72, 4102–4107. (e) He, P.; Lu, Y.;
Hu, Q.-S. Tetrahedron Lett. 2007, 48, 5283–5288. (f) Novodomska`, A.; Dudicova`,
M.; Leroux, F. R.; Colobert, F. Tetrahedron: Asymmetry 2007, 18, 1628–1634.
(g) Lin, S; Lu, X. J. Org. Chem. 2007, 72, 9757–9760. (h) Kuriyama, M.;
Shimazawa, R.; Shirai, R. J. Org. Chem. 2008, 73, 1597–1560.
(7) (a) Hirano, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2005, 7, 4689–
4691. (b) Takahashi, G.; Shirakawa, E.; Tsuchimoto, T.; Kawakami, Y.; Ishikawa,
T. Chem. Commun. 2005, 1459–1461. (c) Arao, T.; Kondo, K.; Aoyama, T.
Tetrahedron Lett. 2007, 48, 4115–4117.
(8) Tomita, D.; Kanai, M.; Shibasaki, M. Chem. Asian J. 2006, 1, 161–166.
(9) Liao, Y.-X.; Xing, C.-H.; He, P.; Hu, Q.-S. Org. Lett. 2008, 10, 2509–
2512.
(1) (a) Suzuki, A. Acc. Chem. Res. 1982, 15, 178–184. (b) Miyaura, N.;
Suzuki, A. Chem. ReV. 1995, 95, 2457–2483. (c) Suzuki, A. J. Organomet. Chem.
1998, 576, 147–168.
(2) (a) Casy, A. F.; Drake, A. F.; Ganellin, C. R.; Mercer, A. D.; Upton, C.
Chirality 1992, 4, 356–366. (b) Spencer, C. M.; Foulds, D.; Peter, D. H. Drugs
1993, 46, 1055–1080. (c) Botta, M.; Summa, V.; Corelli, F.; Pietro, G. D.;
Lombardi, P. Tetrahedron: Asymmetry 1996, 7, 1263–1266.
(10) Reviews: (a) Molander, G. A; Figueroa, R. Aldrichim. Acta. 2005, 38,
49–56. (b) Molander, G. A.; Ellis, N. Acc. Chem. Res. 2007, 40, 275–286. (c)
Stefani, H. A.; Cella, R.; Adriano, S. Tetrahedron 2007, 63, 3623–3658. (d)
Darses, S.; Genet, J.-P. Chem. ReV. 2008, 108, 288–305.
(11) Onak, T. Organoborane Chemistry; Academic Press: New York, 1975.
(12) (a) Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett. 1999,
40, 4289–4292. (b) Darses, S.; Michaud, G.; Genet, J.-P. Eur. J. Org. Chem.
1999, 5, 1875–1883. (c) Chambers, R. D.; Clark, H. C.; Willis, C. J. J. Am.
Chem. Soc. 1960, 82, 5298–5301.
(3) (a) Sakai, M.; Ueda, M.; Miyaura, N. Angew. Chem., Int. Ed. 1998, 37,
3279–3281. (b) Ueda, M.; Miyaura, N. J. Org. Chem. 2000, 65, 4450–4452.
10.1021/jo801352h CCC: $40.75
Published on Web 08/06/2008
2008 American Chemical Society
J. Org. Chem. 2008, 73, 6939–6942 6939