PAPER
Suzuki–Miyaura Coupling
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fully evacuated and backfilled with N2 (3 cycles). 4-Chlorotoluene
(0.5 mmol, 1.0 equiv) and H2O (1.5 mL) were added via syringe.
This batch of Schlenk tube was resealed and magnetically stirred in
a preheated 100 °C oil bath. After the completion of the reaction,
the reaction tubes were allowed to reach r.t. EtOAc (~10 mL), do-
decane (114 μL, internal standard) and H2O (~3 mL) were added.
The organic layer was subjected to GC analysis. The GC yield was
previously calibrated by authentic sample/dodecane calibration
curve.
2007, 72, 3558. (c) Molander, G. A.; Ham, J.; Canturk, B.
Org. Lett. 2007, 9, 821.
(5) For recent selected examples from Molander’s group, see:
(a) Molander, G. A.; Shin, I. Org. Lett. 2013, 15, 2534.
(b) Molander, G. A.; Shin, I. Org. Lett. 2012, 14, 3138.
(c) Molander, G. A.; Fleurt-Brégeot, N.; Hiebel, M.-A. Org.
Lett. 2011, 13, 1694. (d) Molander, G. A.; Hiebel, M.-A.
Org. Lett. 2010, 12, 4876. (e) Molander, G. A.; Cavalcanti,
L. N.; Canturk, B.; Pan, P. S.; Kennedy, L. E. J. Org. Chem.
2009, 74, 7364. (f) Cho, Y. A.; Kim, D. S.; Ahn, H. R.;
Canturk, B.; Molander, G. A.; Ham, J. Org. Lett. 2009, 11,
4330. (g) Molander, G. A.; Febo-Ayala, W.; Jean-Gérard, L.
Org. Lett. 2009, 11, 3830. (h) Molander, G. A.; Jean-Gérard,
L. J. Org. Chem. 2009, 74, 5446. (i) Dreher, S. D.; Lim, S.
E.; Sandrock, D. L.; Molander, G. A. J. Org. Chem. 2009,
74, 3626. (j) Molander, G. A.; Jean-Gérard, L. J. Org. Chem.
2009, 74, 1297. (k) Molander, G. A.; Cooper, D. J. J. Org.
Chem. 2008, 73, 3885. (l) Molander, G. A.; Gormisky, P. E.;
Sandrock, D. L. J. Org. Chem. 2008, 73, 2052.
Biaryls 1; General Procedure for the Suzuki–Miyaura Cou-
pling of Aryl Chlorides
A stock solution of Pd source (2 mol%) with ligand (corresponding
Pd/L ratio) in freshly distilled CH2Cl2 (10 mL) was initially pre-
pared with continuously stirring at r.t. An array of Schlenk tubes
equipped with a Teflon-coated magnetic stirrer bar were evacuated
and backfilled with N2 (3 cycles). The stock solution of Pd with li-
gand (0.5 mL, 0.1 mol% Pd, or please refer to the corresponding Pd
loading from different entries) and Et3N (0.1 mL) were transferred
to an array of Schlenk tubes via syringes. The diluted Pd complex
solution was stirred and warmed using a household hair drier for
about 1 to 2 min until the solvent started boiling. The solvent was
then evaporated under high vacuum. Ar2BF3K (0.75 mmol, 1.5
equiv) and base (1.5 mmol, 3.0 equiv) were added to an array of
Schlenk tubes. Each tube was carefully evacuated and backfilled
with N2 (3 cycles). Aryl chloride (0.5 mmol, 1.0 equiv) and H2O
(1.5 mL) were added via syringe. This batch of Schlenk tube was re-
sealed and magnetically stirred in a preheated 100 °C oil bath. After
the completion of the reaction, the reaction tubes were allowed to
reach r.t. EtOAc (~10 mL) and H2O (~3 mL) were added. The or-
ganic layer was subjected to GC analysis. The filtrate was concen-
trated under reduced pressure. The crude products were purified by
flash column chromatography on silica gel (230–400 mesh) to af-
ford the desired product.
(m) Molander, G. A.; Gormisky, P. E. J. Org. Chem. 2008,
73, 7481. (n) Molander, G. A.; Sandrock, D. L. Org. Lett.
2007, 9, 1597. (o) Molander, G. A.; Vargas, F. Org. Lett.
2007, 9, 203.
(6) For recent selected examples, see: (a) Abel, R.; Aggarwal,
V. K. Angew. Chem. Int. Ed. 2009, 48, 6289. (b) Doucet, H.
Eur. J. Org. Chem. 2008, 2013. (c) Kabalka, G. W.; Zhou,
L.-L.; Naravane, A. Tetrahedron Lett. 2006, 47, 6887.
(d) Harker, R. L.; Crouch, R. D. Synthesis 2007, 25. (e) Wu,
J.; Zhang, L.; Luo, Y. Tetrahedron Lett. 2006, 47, 6747.
(f) Wu, J.; Zhang, L.; Xia, H.-G. Tetrahedron Lett. 2006, 47,
1525. (g) Cella, R.; Cunha, R. L. O. R.; Reis, A. E. S.;
Pimenta, D. C.; Klitzke, C. F.; Stefani, H. A. J. Org. Chem.
2006, 71, 244. (h) Arvela, R. K.; Leadbeater, N. E.; Mack, T.
L.; Kormos, C. M. Tetrahedron Lett. 2006, 47, 217.
(i) Kabalka, G. W.; Al-Masum, M. Tetrahedron Lett. 2005,
46, 6329. (j) Barder, T. E.; Buchwald, S. L. Org. Lett. 2004,
6, 2649. (k) Quach, T. D.; Batey, R. A. Org. Lett. 2003, 5,
4397. (l) Quach, T. D.; Batey, R. A. Org. Lett. 2003, 5, 1381.
(m) Fang, G.-H.; Yan, Z.-J.; Deng, M.-Z. Org. Lett. 2004, 6,
357. (n) Darses, S.; Genet, J.-P. Eur. J. Org. Chem. 2003,
4313.
Acknowledgment
We thank the Research Grants Council of Hong Kong (GRF:
PolyU5010/11P), Shenzhen Strategic New Industry Development
Fund (JCYJ20130401152508653) and State Key Laboratory of
Chirosciences for financial support. F.Y.K. thanks the Croucher
Foundation for the Croucher Senior Research Fellowship (2013).
(7) (a) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous
Media; Wiley-Interscience: New York, 1997. (b) Cornils,
B.; Herrmann, W. A. Aqueous-Phase Organometallic
Catalysis, 2nd ed.; Wiley-VCH: Weinheim, 2004.
Supporting Information for this article is available online
at
(c) Lindström, U. M. Chem. Rev. 2002, 102, 2751.
(d) Tundo, P.; Anastas, P. T. Green Chemistry: Challenging
Perspectives; Oxford University Press: Oxford, 2000.
(e) Nelson, W. M. Green Solvents for Chemistry,
10.1055/s-00000084.SunpfgIpi
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Synthesis 2014, 46, 2826–2832