Table 2 Nickel-catalysed cross-coupling of 1a with aryl tosylates
Notes and references
1 (a) Metal-Catalyzed Cross-Coupling Reactions, ed. A. de Meijere
and F. Diederich, Wiley-VCH, Weinheim, 1998; (b) Metal-
Catalyzed Cross-Coupling Reactions, ed. A. de Meijere and
F. Diederich, Wiley-VCH, Weinheim, 2nd edn, 2004.
2 (a) T. Hiyama, Metal-Catalyzed Cross-Coupling Reactions,
ed. A. de Meijere and F. Diederich, Wiley-VCH, Weinheim,
1998, pp. 421–453; (b) T. Hiyama and E. Shirakawa, Top. Curr.
Chem., 2002, 219, 61; (c) S. E. Denmark and R. F. Sweis, in
Metal-Catalyzed Cross-Coupling Reactions, ed. A. de Meijere and
F. Diederich, Wiley-VCH, Weinheim, 2nd edn, 2004, pp. 163–216;
(d) J. Tsuji, Palladium Reagents and Catalysts, John Wiley & Sons,
Chichester, 2004, pp. 338–351.
Yield of
3a (%)
Entry
TsO–Ar
Time/h
3 (a) J.-Y. Lee and G. C. Fu, J. Am. Chem. Soc., 2003, 125, 5616;
(b) D. A. Powell and G. C. Fu, J. Am. Chem. Soc., 2004, 126, 7788;
(c) N. A. Strotman, S. Sommer and G. C. Fu, Angew. Chem., Int.
Ed., 2007, 46, 3556; (d) X. Dai, N. A. Strotman and G. C. Fu,
J. Am. Chem. Soc., 2008, 130, 3302.
4 (a) Y. Nakao, H. Imanaka, A. K. Sahoo, A. Yada and T. Hiyama,
J. Am. Chem. Soc., 2005, 127, 6952; (b) Y. Nakao, J. Chen,
H. Imanaka, T. Hiyama, Y. Ichikawa, W. L. Duan, R. Shintani
and T. Hayashi, J. Am. Chem. Soc., 2007, 129, 9137; (c) J. Chen,
M. Tanaka, M. Takeda, A. K. Sahoo, A. Yada, Y. Nakao and
T. Hiyama, Bull. Chem. Soc. Jpn., 2010, 83, 554; (d) Y. Nakao,
M. Takeda, T. Matsumoto and T. Hiyama, Angew. Chem., Int.
Ed., 2010, 49, 4447. (Hydroxymethyl)phenyl-substituted silicon
reagents (HOMSi reagents) are available from Advanced Molecular
Technologies Pty Ltd (http://www.amtechpl.com).
5 For palladium-catalysed silicon-based aryl–aryl cross-coupling
with aryl chlorides, see: (a) K.-i. Gouda, E. Hagiwara,
Y. Hatanaka and T. Hiyama, J. Org. Chem., 1996, 61, 7232;
(b) E. Hagiwara, K.-i. Gouda, Y. Hatanaka and T. Hiyama,
Tetrahedron Lett., 1997, 38, 439; (c) H. M. Lee and S. P. Nolan,
Org. Lett., 2000, 2, 2053; (d) T. Koide and A. Mori, Synlett, 2003,
1850; (e) C. Wolf, R. Lerebours and E. H. Tanzini, Synthesis, 2003,
2069; (f) A. K. Sahoo, Y. Nakao and T. Hiyama, Chem. Lett.,
2004, 632; (g) A. K. Sahoo, T. Oda, Y. Nakao and T. Hiyama,
Adv. Synth. Catal., 2004, 346, 1715; (h) C. Wolf and R. Lerebours,
Org. Lett., 2004, 6, 1147; (i) M. Murata, S. Yoshida, S.-i. Nirei,
S. Watanabe and Y. Masuda, Synlett, 2006, 118; (j) J.-H. Li,
C.-L. Deng and Y.-X. Xie, Synthesis, 2006, 969; (k) E. Alacid and
1
2
3
OMe (6a)
Me (6b)
Me (60b)b
F (6c)
CO2Me (6d)
Ac (6e)
CN (6f)
24
24
24
20
20
20
20
72 (4aa)
73 (4ab)
71 (4ab)
73 (4ae)
83 (4ar)
73 (4ah)
64 (4ai)
4c
5c
6c
7c
8
24
62 (4ak)
a
b
c
Isolated yields. Run with p-tolyl methanesulfonate. Run with
Ni(PPh2Me)2Cl2 (5 mol%) and PPh2Me (5 mol%) instead of
Ni(PPh3)2Cl2 (5 mol%) and PPh3 (5 mol%).
catalysts in the presence of an excess amount of highly
nucleophilic and expensive TBAF as a fluoride activator.6
After brief tuning of the reaction conditions, we found that
the reaction of 1a (1.3 mmol) with unactivated 4-methoxy-
phenyl tosylate (6a, 1.0 mmol) proceeded smoothly in the
presence of Ni(PPh3)2Cl2 (5 mol%), Zn (10 mol%), extra PPh3
(5 mol%), PCy3 (15 mol%), and Cs2CO3 (2.0 mmol) in
acetone–DMF (2 : 1) at 80 1C for 24 h to give 4aa in 72%
yield (entry 1 of Table 2). A range of functionalised aryl
tosylates reacted with 1a to give the corresponding biaryls
(entries 2–8). An aryl mesylate also participated in the reaction
to give biaryl 4ab in comparable yield (entry 3).
C. Najera, Adv. Synth. Catal., 2006, 348, 945; (l) M. Endo,
´
T. Sakurai, S. Ojima, T. Katayama, M. Unno, H. Matsumoto,
S. Kowase, H. Sano, M. Kosugi and K. Fugami, Synlett, 2007,
749; (m) L. Ackermann, C. J. Gschrei, A. Althammer and
M. Riederer, Chem. Commun., 2006, 1419; (n) S. E. Denmark,
J. D. Baird and C. S. Regens, J. Org. Chem., 2008, 73, 1440;
(o) S. E. Denmark, R. C. Smith, W.-T. T. Chang and
J. M. Muhuhi, J. Am. Chem. Soc., 2009, 131, 3104;
(p) S. E. Denmark and J. D. Baird, Tetrahedron, 2009, 65, 3120;
(q) X. Zhang, Q. Xia and W. Chen, Dalton Trans., 2009, 7045;
(r) S. M. Raders, J. V. Kingston and J. G. Verkade, J. Org. Chem.,
2010, 75, 1744.
6 For palladium-catalysed silicon-based aryl–aryl cross-coupling
with aryl tosylates and mesylates, see: (a) L. Zhang and J. Wu,
J. Am. Chem. Soc., 2008, 130, 12250; (b) L. Zhang, J. Qing,
P. Yang and J. Wu, Org. Lett., 2008, 10, 4971; (c) C. M. So,
H. W. Lee, C. P. Lau and F. Y. Kwong, Org. Lett., 2009, 11, 317.
7 K. Tamao, Y. Nakagawa, H. Arai, N. Higuchi and Y. Ito, J. Am.
Chem. Soc., 1988, 110, 3712.
In summary, we have demonstrated that newly developed
arylsilane reagents 1 effect the nickel-catalysed silicon-based
aryl–aryl cross-coupling reaction for the first time. Use of
highly stable, readily accessible, and recyclable aryl(trialkyl)-
silanes activated by a mild carbonate base in the presence of a
nickel catalyst prepared in situ from inexpensive nickel(II) salts
would merit synthetic organic chemists both in academia and
industry to perform chemoselective biaryl synthesis.
The authors are grateful to Professor Masaki Shimizu for
X-ray crystallographic analysis. This work has been supported
financially by a Grant-in-Aid for Priority Areas ‘‘Synergy of
Elements’’ from MEXT. S.T. acknowledges the JSPS for a
postdoctoral fellowship.
8 See ESIw for details.
9 (a) V. Percec, G. M. Golding, J. Smidrkal and O. Weichold, J. Org.
Chem., 2004, 69, 3447; (b) V. Kogan, Tetrahedron Lett., 2006, 47,
7515.
10 For a review, see: A. Littke, in Modern Arylation Methods,
ed. L. Ackermann,Wiley-VCH, Weinheim, 2009, pp. 25–67.
c
This journal is The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 307–309 309