Communications
Webber, M. D. Varney, M. R. Reddy, K. K. Lewis, V. Kathardekar, H. Maz-
diyasni, J. Deal, D. Nguyen, K. M. Welsh, S. Webber, A. Johnston, D. A.
Matthews, W. W. Smith, C. A. Janson, R. J. Bacquet, E. F. Howland, C. L. J.
Booth, S. M. Herrmann, R. W. Ward, J. White, C. A. Bartlett, C. A. Morse, J.
O’Neill, D. Liu, E. Rands, J. C. Culberson, R. B. Lobell, K. S. Koblan, N. E.
Kohl, J. B. Gibbs, A. I. Oliff, S. L. Graham, G. D. Hartman, Bioorg. Med.
H2O plays a significant role in the reaction as it helps dissolve
the reagents and facilitates the formation of complex 5. The
basicity of base and amount of H2O are important as they
both affect the concentration of hydroxide ion. With the same
amount of H2O, a weak base such as Na2CO3 (Table 1, entry 9)
is not efficient for the formation of complex 5, owing to the
low concentration of hydroxide ion, while a strong base such
as KOH (Table 1, entry 12) may facilitate the formation of acid
7 and its sulfonate 8. Although the proposed catalytic mecha-
nism was not confirmed by experimental data, it is supported
by literature results[14a,17] and the color change observed
during the reactions: the solution of complex [LCuIBr] in CH2Cl2
was deep red; addition of H2O followed by arylsulfonyl chlo-
ride to the solution turned the color from deep red to green;
after addition of fully mixed base and arylboronic acid, the
mixture turned back to deep red when the reaction was com-
plete.
[2] a) J. B. McMahon, R. J. Gulakowski, O. S. Weislow, R. J. Schultz, V. L. Nar-
ayanan, D. J. Clanton, R. Pedemonte, F. W. Wassmundt, R. W. Buckheit,
Williams, T. M. Ciccarone, S. C. MacTough, C. S. Rooney, S. K. Balani, J. H.
36, 1291–1294; c) N. Neamati, A. Mazumder, H. Zhao, S. Sunder, T.
Burke, R. J. Schultz, Y. Pommier, Antimicrob. Agents Chemother. 1997, 41,
385–393.
[3] a) P. Prasit, Z. Wang, C. Brideau, C. C. Chan, S. Charleson, W. Cromlish, D.
Ethier, J. F. Evans, A. W. Ford-Hutchinson, J. Y. Gauthier, R. Gordon, J.
Guay, M. Gresser, S. Kargman, B. Kennedy, Y. Leblanc, S. LØger, J. Manci-
ni, G. P. O’Neill, M. Ouellet, M. D. Percival, H. Perrier, D. Riendeau, I.
Rodger, P. Tagari, M. ThØrien, P. Vickers, E. Wong, L. J. Xu, R. N. Young, R.
Zamboni, S. Boyce, N. Rupniak, M. Forrest, D. Visco, D. Patrick, Bioorg.
Corley, M. Journet, D.-W. Cai, M. Palucki, J. Wu, R. D. Larsen, K. Rossen,
8415–8420; c) M. Pal, V. Rao Veeramaneni, M. Nagabelli, S. Rao Kalleda,
In summary, we have developed an efficient and convenient
method for the synthesis of diaryl sulfones. The catalytic
system is applicable to both electron-rich and electron-defi-
cient arylsulfonyl chlorides and arylboronic acids. However, the
presence of electron-withdrawing groups generally deactivated
the substrates and resulted in lower yields and longer reaction
times. The basicity of base and the presence of ligand and H2O
played an important role in the reactions.
[4] A.-M. Faucher, P. W. White, C. Brochu, C. Grand-Maître, J. Rancourt, G.
[5] T. Otzen, E. G. Wempe, B. Kunz, R. Bartels, G. Lehwark-Yvetot, W. Hänsel,
Experimental Section
General procedure for CuI-catalyzed cross-coupling reac-
tions
6525–6528; b) A. Ivachtchenko, E. Golovina, M. Kadieva, O. Mitkin, S.
Uchiyama, T. Kano, Synthesis 1984, 1984, 323–325.
At room temperature (258C) in open air to the deep red solution
of complex [(phen)CuIBr] (0.15 mmol) in CH2Cl2 (3 mL) was added
H2O (25 mL) followed by arylsulfonyl chloride (1.5 mmol) to gener-
ate green suspension, to which was added the fully mixed arylbor-
onic acid (1.8 mmol) and base (3.0 mmol) in three portions. The re-
sulting mixture was stirred until it turned to deep red indicating
that the reaction was complete. After the reaction was done, for
Table 1, the resulting mixture was filtered, and the solution was an-
alyzed by GC using 4-methylphenyl mesylate as standard; for
Tables 2 and 3, to the mixture was added anhydrous MgSO4 and
silica gel, and the solvent was removed by rotary evaporation
under reduced pressure to give a mixture that was purified by
flash chromatography on silica gel with ethyl acetate-hexanes (0–
20% ethyl acetate in hexanes) as eluents to afford the correspond-
ing diaryl sulfone.
C. Ma, Synthesis 2007, 2007, 2951–2956; c) S. Cacchi, G. Fabrizi, A. Gog-
Reeves, S. Rodriguez, H. Lee, N. Haddad, D. Krishnamurthy, C. H. Sena-
[13] T. Zhou, Z.-C. Chen, J. Chem. Res. Synop. 2000, 474–475.
Zeng, Z. Wei, D. Zhao, T. Kang, W. Zhang, M. Yan, M. Luo, Synlett 2006,
12, 1891–1894.
Acknowledgements
We thank the Robert A. Welch Foundation (Grant No. V-1815) for
financial support of this research.
Keywords: arylboronic acids · arylsulfonyl chlorides · copper ·
cross-coupling reactions · diaryl sulfones
Received: February 23, 2015
449–462; b) Z.-Y. Sun, E. Botros, A.-D. Su, Y. Kim, E. Wang, N. Z. Baturay,
Published online on April 21, 2015
ChemCatChem 2015, 7, 1539 – 1542
1542
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