Z.-Y. Tang et al. / Tetrahedron Letters 47 (2006) 2427–2430
2429
a
Table 4. Ni(0)/2-Catalyzed Suzuki–Miyaura cross-couplings
Tetrahedron 2000, 56, 7163–7171; (c) Percec, V.; Bae,
J.-Y.; Zhao, M.; Hill, D. H. J. Org. Chem. 1995, 60, 176–
185.
. For recent reviews: (a) Miyaura, N. Topics Curr. Chem.
2002, 219, 11–59; (b) Suzuki, A. J. Organomet. Chem.
4
%Ni(COD)
2
/12% 2
Ar X
Entry
+
(HO)2B Ar'
Ar -Ar'
K PO , THF, r.t., 48 h
3
4
2
3
0
b
Ar–X
Ar –B(OH)
2
Yield (%)
1
999, 576, 147–168.
. For a recent review: Littke, A. F.; Fu, G. C. Angew.
Chem., Int. Ed. 2002, 41, 4176–4211.
1
2
3
MeO
MeO
MeO
OTs
Cl
Cl
B(OH)2
39
24
B(OH)2
B(OH)2
4. Recent examples of Suzuki cross-coupling reactions
involving aryl chlorides as substrates: (a) Barder, T. E.;
Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am.
Chem. Soc. 2005, 127, 4685–4696; (b) Singh, R.; Viciu, M.
S.; Kramareva, N.; Navarro, O.; Nolan, S. P. Org. Lett
c
23
4
5
6
Cl
Cl
Cl
B(OH)2
32
2
005, 7, 1829–1832; (c) Altenhoff, G.; Goddard, R.;
Lehmann, C. W.; Glorius, F. J. Am. Chem. Soc. 2004,
26, 15195–15201; (d) Stambuli, J. P.; Kuwano, R.;
Hartwig, J. F. Angew. Chem., Int. Ed. 2003, 41, 4746–
748; (e) Hu, Q.-S.; Lu, Y.; Tang, Z.-Y.; Yu, H.-B. J. Am.
d
69.5
B(OH)2
B(OH)2
1
c,d
66
4
a
Reaction conditions: aryl sulfonates (1.0 equiv), arylboronic acids
1.5 equiv), K PO (3 equiv), THF (2 ml), room temperature.
Chem. Soc. 2003, 125, 2856–2857; (f) Jensen, J. F.;
Johannsen, M. Org. Lett. 2003, 5, 3025–3028; (g) Alten-
hoff, G.; Goddard, R.; Lehmann, C. W.; Glorius, F.
Angew. Chem., Int. Ed. 2003, 42, 3690–3693; (h) Navarro,
O.; Kelly, R. A., III; Nolan, S. P. J. Am. Chem.
Soc. 2003, 125, 16194–16195; (i) Pickett, T. E.; Roca, F.
X.; Richards, C. J. J. Org. Chem. 2003, 68, 2592–2599; (j)
Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.; Trudell,
M. L.; Nolan, S. P. Organometallics 2002, 21, 2866–2873;
(
3
4
b
c
Isolated yields (average of two runs).
Recovered 2 was used.
Reaction temperature: 60 °C.
d
at 60 °C, and 2 was recoverable and reusable (Table 4,
entries 5 and 6).
(
k) Kataoka, N.; Shelby, Q.; Stambuli, J. P.; Hartwig, J. F.
J. Org. Chem. 2002, 67, 5553–5566; (l) Gstottmayr, C. W.
K.; Bohm, V. P. W.; Herdtweck, E.; Grosche, M.;
Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41,
In summary, we have demonstrated that readily avail-
able ferrocenylmethylphosphine can be employed as an
efficient ligand for room temperature Ni(0)-catalyzed
Suzuki–Miyaura cross-couplings of aryl arenesulfo-
nates. The catalyst system was also found to catalyze
the Suzuki–Miyaura couplings of deactivated aryl chlo-
rides at room temperature. The polymeric ferrocenyl-
methylphosphine was found to be an efficient ligand
for the Ni(0)-catalyzed cross-coupling of aryl chlorides
with arylboronic acids, and recoverable and reusable.
1
363–1365; (m) Stauffer, S. R.; Lee, S.; Stambuli, J. P.;
Hauck, S. I.; Hartwig, J. F. Org. Lett. 2000, 2, 1423–
1426.
5. Room temperature cross-coupling of one example of
electron-deficient aryl tosylate with lithium arylborates
was reported: Kobayashi, Y.; Mizojiri, R. Tetrahedron
Lett. 1996, 37, 8531–8534.
. Lakshman, M. K.; Thomson, P. F.; Nuqui, M. A.; Hilmer,
J. H.; Sevova, N.; Boggess, B. Org. Lett. 2002, 4, 1479–
6
1
482.
7
8
. Ngyuen, H. N.; Huang, X.; Buchwald, S. L. J. Am. Chem.
Soc. 2003, 125, 11818–11819.
Acknowledgements
. (a) Percec, V.; Golding, G. M.; Smidrkal, J.; Weichold, O.
J. Org. Chem. 2004, 69, 3447–3452; (b) Percec, V.; Bae,
J.-Y.; Hill, D. H. J. Org. Chem. 1995, 60, 1060–1065.
. Suzuki–Miyaura coupling reactions involving aryl mesy-
lates: (a) Percec, V.; Bae, J.-Y.; Zhao, M.; Hill, D. H. J.
Org. Chem. 1995, 60, 1066–1069. Also see Refs. 5 and 8;
Suzuki–Miyaura coupling reactions involving vinyl tosy-
lates: (b) Wu, J.; Zhu, Q.; Wang, L.; Fathi, R.; Yang, Z. J.
Org. Chem. 2003, 68, 670–673; (c) Wu, J.; Wang, L.; Fathi,
R.; Yang, Z. Tetrahedron Lett. 2002, 43, 4395–4397; (d)
Huffman, M. A.; Yasuda, N. Synlett 1999, 471–473.
We gratefully thank the NIH (GM69704) for financial
support. Partial support from the PSC-CUNY Research
Award programs, NYSTAR-Cart program for ‘Center
for Engineered Polymeric Materials’, and GRTI (The
Graduate Research and Technology Initiative) Grants
are also gratefully acknowledged. This work also bene-
fited from the NSF-REU program at CSI and the CSI
Deans Offices Undergraduate Summer Research
Program.
9
1
0. For other coupling reactions involving aryl arenesulfo-
nates: (a) Roy, A. H.; Hartwig, J. F. J. Am. Chem. Soc.
2003, 125, 8704–8705; (b) Huang, X.; Anderson, K. W.;
Zim, D.; Jiang, L.; Klapars, A.; Buchwald, S. L. J. Am.
Chem. Soc. 2003, 125, 6653–6655; (c) Gelman, D.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2003, 42, 5993–
Supplementary data
Experiment procedures and characterization of the
cross-coupling products. Supplementary data associated
5
6
996; (d) Wu, J.; Liao, Y.; Yang, Z. J. Org. Chem. 2003,
8, 3642–3645; (e) Furstner, A.; Leitner, A.; Mendez, M.;
Krause, H. J. Am. Chem. Soc. 2002, 124, 13856–13863; (f)
Bolm, C.; Hildebrand, J. P.; Rudolph, J. Synthesis 2000,
9
11; (g) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc.
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