4
Tetrahedron Letters
1
For reviews, see: (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95,
2457. (b) Suzuki, A. J. Organomet. Chem. 1999, 576, 147. (c)
Miyaura, N. Topics in Current Chem. 2002, 219, 11. (d) Molander,
G, A; Ellis, N. Acc. Chem. Res. 2007, 40, 275.
electrophiles employed in Suzuki coupling. For this study, an
equimolar mixture of 1a and 8 with 3 mol% Pd(PPh3)2Cl2 in t-
BuOH was treated with 1 equiv. of boronic acid. Upon
completion, the reactions were monitored by GCMS FID. The
experimental results revealed that ArOPFBs have comparable
reactivity to iodides and bromides, but more reactive than chloro,
tosylate, mesylate and triflate intermediates (Table 6).
2
3
(a) Kotha, S.; Lahiri, K.; Kashinath, D. Tetarhedron. 2002, 58,
9633. (b) Lightowler, S.; Hird, M. Chem. Matter. 2005, 17, 5538.
(a) Smith, G, B.; Dezeny, G, C.; Hughes, D, L.; King, A, O.;
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W, H.; de Leeuw, P. W. J. Hypertens. 1999, 17, 873. (c) Goa, K, L.;
Wagstaff, A, J. Drugs 1996, 51, 820.
Table 6: Crossover Experiments of ArOPFBs with other
Electrophiles.
a
4
4. (a) Littke, A, F.; Fu G, C. Angew. Chem. Int. Ed. 2002, 41,
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So, C, M.; Yeung, C, C.; Lau, C, P.; Kwong, F, Y. J. Org. Chem.
2008, 73, 7803. (d) Hoshi, T.; Nakazawa, T.; Saitoh, I.; Mori, Y.;
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2063. (e) Fujihara, T.; Yoshida, S.; Terao, J.; Tsuji, Y. Org. Lett.
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(a) Scott, W, J.; Crisp, G, T.; Stille, J, K. J. Am. Chem. Soc. 1984,
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Synthesis 1993, 735. (d) Hartwig, J, F. Angew. Chem., Int. Ed.
1998, 37, 2046. (e) Littke, A, F.; Dai, C.; Fu, G, C. J. Am. Chem.
Soc. 2000, 122, 4020.
(a) Hayashi, T.; Katsuro, Y.; Okamoto, Y.; Kumada, M.
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Huang, z.; Dong, j.; Sharpless, k, b.; Li, x.; Jiang, b. Org. Lett.
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3611. (f) Gauthier, D.; Beckendorf, S.; Gøgsig, T. M.; Lindhardt, A,
T.; Skrydstrup, T. J. Org. Chem. 2009, 74, 3536. (g) Yoshikai, N.;
Matsuda, H.; Nakamura, E. J. Am. Chem. Soc. 2009, 131, 9590. (h)
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aReaction conditions: 1(0.5 mmol), 8(0.5 mmol), Boronic acid
(0.5 mmol), Pd(PPh3)2Cl2(3 mol%), K3PO4.H2O (3 equiv), t-
BuOH (2 mL), RT, 12h. bIsolated yield.
We have also demonstrated the synthesis of aryl boronate
from pentafluorobenzene sulfonate and its subsequent conversion
to biaryls by a one pot process as shown in Scheme 1.
7
8
9
So, C, M.; Lau, C, P.; Chan, A, S, C.; Kwong, F, Y. J. Org. Chem.
2008, 73, 7731.
(a) Roger, J.; Doucet, H. Org. Biomol. Chem. 2008, 6, 169. (b)
Doucet, H. Eur. J. Org. Chem. 2008, 2013.
Molander, G, A.; Petrillo, D, E. Org. Lett. 2008, 10, 1795.
10 (a) Düfert, M, A.; Billingsley, K, L.; Buchwald, S, L. J. Am. Chem.
Soc. 2013, 135, 12877. (b) Billingsley, K, L.; Anderson, K, W.;
Buchwald, S, L. Angew. Chem. Int. Ed. 2006, 45, 3484.
Scheme 1: One pot synthesis of biaryls.
11 (a) Glorius, F.; Altenhoff, G.; Goddard, R.; Lehmann, C, W.
Angew. Chem. Int. Ed. 2003, 42, 3690. (b) Organ, M, G.; Calimsiz,
S.; Sayah, M.; Hoi, K, H.; Lough, A, J. Angew. Chem. Int. Ed.
2009, 48, 2383. (c) Tu, T.; Sun, Z.; Fang, W.; Xu, M.; Zhou, Y.
Org. Lett. 2012, 14, 4250. (d) Ackermann, L.; Potukuchi, H, K.;
Althammer, A.; Born, R.; Mayer. P. Org. Lett. 2010, 12, 1004. (e)
Yin, Y.; Rainka, M, P.; Zhang, X. –X.; Buchwald, S, L. J. Am.
Chem. Soc. 2002, 124, 1162.
12 (a) Martin, R.; Buchwald. S, L. Acc. Chem. Res. 2008, 41, 1461. (b)
Christmann, U.; Vilar, R. Angew. Chem. Int. Ed. 2005, 44, 366. (c)
Sajith, A, M.; Muralidharan, A. Tetrahedron Lett. 2012, 53, 5206.
(d) Hartwig, J, F. Inorg. Chem. 2007, 46, 1936.
13 For examples of Suzuki reactions with alkylboron derivatives: (a)
Miyaura, N.; Ishiyama, T.; Ishikawa, M.; Suzuki, A. Tetrahedron
Lett. 1986, 27, 6369. (b) Wright, S, W.; Hageman, D, L.; McClure,
L, D. J. Org. Chem. 1994, 59, 6095. (c) Guiles, J, W.; Johnson, S,
G.; Murray, W, V. J. Org. Chem. 1996, 61, 5169. (d) Botella, L.;
Najera, C.; J. Organomet. Chem. 2002, 46, 663. (e) Kataoka, N.;
Shelby, Q.; Stambuli, J, P.; Hartwig, J, F. J. Org. Chem. 2002, 67,
5553. (f) Molander, G, A.; Yun, C. –S. Tetrahedron 2002, 58,
1465.
3. Conclusion
In conclusion, we have disclosed a new class of palladium-
catalyzed cross-coupling partners involving aryl/heteroaryl
pentafluorobenzenesulfonate. The ease of preparation of these
bench stable intermediates, use of Pd(PPh3)2Cl2 as mild catalyst,
rapid reaction conditions, wide substrate scope, high
chemoselectivity and facile synthesis of highly ortho substituted
biaryls make this method especially attractive. Further
investigations into the utility of these electrophiles in other
metal-mediated processes are currently underway and will be
reported in due course.
Acknowledgements
The authors are thankful to Dr. Sathya Shanker, Dr. Sridevi
Bashyam and Dr. Venkatesan Srinivasan of Syngene Intl. ltd. for
their valuable suggestions during the preparation of the
manuscript.
14 Khaddour, Z.; Akraw, O, A.; Hamdy, A, M.; Suleiman, A.; Jamous,
K.; Villinger, A.; Langer, P. Tetrahedron Lett. 2015, 56, 554.
Supplementary data
Supplementary data (Copies of the 1H and 13C NMR spectra of
the products) associated with this article can be found, in the
online version.
References