Chemoselective Cross-Coupling of Arylboronic Acids in Water
mmol) was added. A dark-blue solution was obtained immedi-
ately, which was stirred at room temperature. After 6 h, this solu-
tion was filtered to remove excess copper salt, which precipitated
as a blue solid (copper hydroxide). To this blue solution was added
ethanol (ca. 400 mL) until a light-blue suspension was formed,
which was filtered, and the residue washed with ethanol and air-
dried at room temperature. This complex was ground into a fine
powder before use as catalyst.
3
[3] a) R. A. Nelson Jr., J. A. Hope, G. M. Luedemann, L. E. Mc-
Daniel, C. P. Schaffner, J. Antibiot. 1986, 39, 335; b) M. Ezkai,
M. Iwami, M. Yamashita, S. Hashimoto, T. Komori, K. Ume-
hara, Y. Mine, M. Kohsaka, H. Aoki, H. Imanaka, J. Antibiot.
1
985, 38, 1453.
[
4] a) F. Ullmann, Ber. Dtsch. Chem. Ges. 1903, 36, 2389–2391; b)
F. Ullmann, Ber. Dtsch. Chem. Ges. 1904, 37, 853–857; c) I.
Goldberg, Ber. Dtsch. Chem. Ges. 1906, 39, 1691–1696.
[
5] a) Y. Miyake, M. Wu, M. J. Rahman, Y. Kuwatani, M. Iyoda,
J. Org. Chem. 2006, 71, 6110; b) X. Xu, D. Cheng, W. Pei, J.
Org. Chem. 2006, 71, 6637; c) Z. Xu, J. Mao, Y. Zhang, Catal.
Commun. 2008, 9, 97; d) G. Cahiez, A. Moyeux, J. Buendia, C.
Duplais, J. Am. Chem. Soc. 2007, 129, 13788; e) M. K. Robin-
son, V. S. Kochurina, J. M. Hanna, Tetrahedron Lett. 2007, 48,
General Procedure for the Homocoupling of Arylboronic Acids: To
a mixture of Cu –β-CD (0.01 mmol, 13 mg, in this complex the
2
number of water molecules has not been exactly determined so far,
therefore we estimate its molecular weight to be 1300 mg/mmol)
in DMF (1 mL), was added arylboronic acid (0.2 mmol), and the
resulting mixture was stirred at 25–90 °C for 5–48 h. Water (20 mL)
was added to the reaction mixture, which was extracted with
7687.
[
6] a) N. Miyaura, A. Suzuki, Main Group Met. Chem. 1987, 10,
295–300; b) D. J. Koza, E. Carita, Synthesis 2002, 2183–2186;
c) G. W. Kabalka, L. Wang, Tetrahedron Lett. 2002, 43, 3067–
3068.
CH
Na
2
Cl
SO
2
(2ϫ20 mL), and the combined extracts dried with
The product was purified immediately by flash
2
4
.
chromatography (silica gel 60; particle size 230–400 mesh; n-hex-
ane/EtOAc) to afford biaryls 2a–p in 31–83% isolated yields. All
products are known, and most are commercially available (see the
Supporting Information).
[7] a) A. Suzuki, “Cross coupling reaction of organoboron com-
pounds with organic halides” in Metal-catalysed Cross-cou-
pling Reactions (Eds.: F. Diederich, P. T. Stang), Wiley-VCH,
Weinheim, 1998; b) S. P. Stanforth, Tetrahedron 1998, 54, 263–
303.
General Procedure for the Preparation of Phenols of Arylboronic
Acid: To a solution of Cu –β-CD (65 mg, 0.05 mmol) in distilled
2
water (3 mL) was added arylboronic acid (1 mmol), and the re-
sulting mixture was stirred at room temperature for 4–20 h (the
light-blue color became light-green). The reaction mixture was ex-
tracted with dichloromethane (2ϫ10), and the combined extracts
[8] a) N. Kirai, Y. Yamamoto, Eur. J. Org. Chem. 2009, 1864–1867;
b) J. Mao, Q. Hua, G. Xie, Z. Yao, D. Shi, Eur. J. Org. Chem.
2
009, 2262–2266; c) F. V. Singh, H. A. Stefani, Tetrahedron
Lett. 2010, 51, 863–867.
[
9] a) J. P. Parrish, Y. C. Jung, R. J. Floyd, K. W. Jung, Tetrahedron
Lett. 2002, 43, 7899–7902; b) L. M. Klingensmith, N. E. Lead-
beater, Tetrahedron Lett. 2003, 44, 765–768; c) Y. Yamamoto,
R. Suzuki, K. Hattori, N. Nishiyama, Synlett 2006, 1027–1030.
10] a) C. Amatore, C. Cammoun, A. Jutand, Eur. J. Org. Chem.
2 4
were dried with Na SO . The solution was cooled to 0 °C before
GC injection. All the phenols are known, and the products corre-
lated with commercially available samples in gas chromatographic
analysis (50–96% GC yield).
[
[
[
2008, 4567–4570; b) K. Mitsudo, T. Shiraga, H. Tanaka, Tetra-
hedron Lett. 2008, 49, 6593–6595.
11] a) A. Suzuki, J. Organomet. Chem. 1999, 576, 147–168; b)
K. A. Smith, E. M. Campi, W. R. Jackson, S. Marcuccio,
C. G. M. Naeslund, G. B. Deacon, Synlett 1997, 131–132.
12] a) A. W. Thomas, S. V. Ley, Angew. Chem. 2003, 115, 5558;
Angew. Chem. Int. Ed. 2003, 42, 5400–5449 and references cited
thereinb) J.-B. Lan, G.-L. Zhang, X.-Q. Yu, J.-S. You, L. Chen,
M. Yan, R.-G. Xie, Synlett 2004, 1095–1097; c) M. L. Kantam,
G. T. Venkanna, C. Sridhar, B. Sreedhar, B. M. Choudary, J.
Org. Chem. 2006, 71, 9522–9524; d) G. Cheng, M. Luo, Eur. J.
Org. Chem. 2011, 2519–2523; e) J. X. Qiao, P. Y. S. Lam, Syn-
thesis 2011, 829.
General Procedure for C–N Coupling of Arylboronic Acid with
Amines: To a mixture of Cu
(
(
2
–β-CD (65 mg, 0.05 mmol) and amine
3 mmol) in distilled water (2 mL) was added arylboronic acid
1 mmol), and the resulting mixture was stirred at room tempera-
ture for 8–24 h. The reaction mixture was then diluted with water
20 mL), extracted with dichloromethane (2ϫ20), and the com-
bined extracts were dried with Na SO . The product was purified
immediately by flash chromatography (silica gel 60; particle size
(
2
4
230–400 mesh; n-hexane/EtOAc) to afford arylamines 4a–q in 69–
93% isolated yields (see the Supporting Information).
[
13] A. S. Demir, O. Reis, M. Emrullahoglu, J. Org. Chem. 2003,
Supporting Information (see footnote on the first page of this arti-
68, 10130–10134.
1
13
cle): Details of analytical data of the products, and H and
C
[14] C. Gonzalez-Arellano, A. Corma, M. Iglesias, S. Sanchez,
Chem. Commun. 2005, 1990–1992.
NMR spectra of the coupling products 4.
[
[
15] B. Kaboudin, T. Haruki, T. Yokomatsu, Synthesis 2011, 91–95.
16] a) K. Surendra, N. S. Krishnaveni, K. R. Rao, Chem. Commun.
Acknowledgments
2
005, 669; b) Y. Kang, L. Zhou, X. Li, J. Yuan, J. Mater. Chem.
2
011, 21, 3704–3710; c) B. H. Han, S. Polarz, M. Antonietti,
The authors gratefully acknowledge support by the Institute for
Advanced Studies in Basic Sciences (IASBS) Research Council un-
der grant no. G2010IASBS120.
Chem. Mater. 2001, 13, 3915–3919; d) F. Hapitot, A. Ponchel,
S. Tilloy, E. Monflier, C. R. Chim. 2011, 14, 149–166; e) F.
Hapiot, J. Lyskawa, H. Bricout, S. Tilloy, E. Monflier, Adv.
Synth. Catal. 2004, 346, 83–89; f) L. Strimbu, J. Liu, A. E.
Kaifer, Langmuir 2003, 19, 483–485; g) J. D. Senra, L. F. B.
Malta, M. E. H. M. da Costa, R. C. Michel, L. C. S. Aguiar,
A. B. C. Simas, O. A. C. Antunes, Adv. Synth. Catal. 2009, 351,
2411–2422; h) A. Cassez, A. Ponchel, F. Hapiot, E. Monflier,
Org. Lett. 2006, 8, 4823–4826.
[
1] a) H. Yoshida, Y. Yamaryo, J. Ohshita, A. Kunai, Tetrahedron
Lett. 2003, 44, 1541; b) M. S. Wong, X. L. Zhang, Tetrahedron
Lett. 2001, 42, 4087; c) A. Lei, X. Zhang, Tetrahedron Lett.
2002, 43, 2525; d) F. V. Singh, R. Vatsyayan, U. Roy, A. Goel,
Bioorg. Med. Chem. Lett. 2006, 16, 2734; e) H. Meier, Angew.
Chem. 2005, 117, 2536; Angew. Chem. Int. Ed. 2005, 44, 2482–
[17] a) E. Z. Messmer, Phys. Chem. 1927, 126, 369; b) Y. Matsui, T.
Kurita, Y. Date, Bull. Chem. Soc. Jpn. 1972, 45, 3229; c) Y.
Matsui, T. Kurita, M. Yagi, T. Okayama, K. Mochida, Y. Date,
Bull. Chem. Soc. Jpn. 1975, 48, 2187; d) K. Mochida, Y. Mat-
sui, Chem. Lett. 1976, 963; e) Y. Matsui, K. Kinugawa, Bull.
CHem. Soc. Jpn. 1985, 58, 2981; f) E. Norkus, G. Grinciene,
2506.
[
2] G. Wu, H. F. Guo, K. Gao, Y. Liu, K. F. Bastow, S. L. Morris-
Natschke, K. H. Lee, L. Xie, Bioorg. Med. Chem. Lett. 2008,
18, 5272.
Eur. J. Org. Chem. 2011, 6656–6662
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6661