Page 5 of 6
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
ARTICLE
S8 in the presence of a dual metal catalytic system (Pd/Cu) has been
presented in Scheme 2 which includes two cycles.
DOI: 10.1039/C9OB00313D
has been prepared with support from RUDN University
Program 5-100.
Free-phenol firstly reacts with activating agents (acetic anhydride,
tosyl chloride or trifluoromethanesulfonyl chloride) to produce
phenolic intermediates C1. An “arylpalladium” specie C2 is then
formed from the reaction of C1 with palladium followed by
oxidative addition and C-O bond cleavage. Simultaneously, in
another cycle, the organocopper thiolate complex intermediate C3
is formed from aryl boronic acid, S8, and CuI. [15d] Subsequently,
intermediate C3 undergoes transmetallation with intermediate C2
to produce intermediate C4. [18] Finally, the desired product DP is
obtained from the reductive elimination of the key intermediate C4
and restarts the cycle.
Notes and references
‡ Footnotes relating to the main text should appear here. These
might include comments relevant to but not central to the
matter under discussion, limited experimental and spectral data,
and crystallographic data.
§
1
(a) X. Fan, X.-M. Cui, Y.-H. Guan, L.-A. Fu, H. Lv, K. Guo, and
H.-B. Zhu, Eur. J. Org. Chem. 2014, 3, 498; (b) A. J. M. Miller,
W. Kaminsky, and K. I. Goldberg, Organometallics. 2014, 33,
1245; (c) G. Tan, Szilvási, T. S. Inoue, B. Blom, and M. Driess,
J. Am. Chem. Soc. 2014, 136, 9732.
(a) S. Pasquini, C. Mugnaini, C. Tintori, M. Botta, A. Trejos, R.
K. Arvela, M. Larhed, M. Witvrouw, M. Michiels, F. Christ, Z.
Debyser, and F. Corelli, J. Med. Chem. 2008, 51, 5125; (b) A.
Gangjee, Y. B. Zeng, T. Talreja, J. J. McGuire, R. L. Kisliuk, and
S. F. Queener, J. Med. Chem. 2007, 50, 304; (c) A.-M.
Faucher, P.W. White, C. Brochu, C.G. Maitre, J. Rancourt, and
G. Fazal, J. Med.Chem. 2004, 47, 18.
2
Ar1 OH
Z-Cl
PdII
Ar1 OZ Z= -SO2CF3
S
Ar1
Ar
Pd0
-SO2(4-me-Ph)
DP
C1
-OAc
OA
RE
3
4
C. M. Rayner, Advances in Sulfur Chemistry, Vol. 2; JAI Press:
Greenwich, CT, 2000.
Ar1 Pd
S
Ar1 PdII OZ
Pd
(a) P. Leowanawat, N. Zhang, and V. Percec, J. Org. Chem.
2012, 77, 1018; (b) K. W. Quasdorf, X. Tian, and N. K. Garg, J.
Am. Chem. Soc. 2008, 130, 14422; (c) B.-T. Guan, Y. Wang, B.-
J. Li, D.-G. Yu, and Z.-J. Shi, J. Am. Chem. Soc. 2008, 130,
14468; (d) M. Baghbanzadeh, C. Pilger, and C. O. Kappe, J.
Org. Chem. 2011, 76, 1507; (e) K. W. Quasdorf, M. Riener, K.
V. Petrova, and N. K. Garg, J. Am. Chem. Soc. 2009, 131,
17748; (f) R. Kuwano, and R. Shimizu, Chem. Lett. 2011, 40,
913; (g) Y.-L. Zhao, Y. Li, Y. Li, L.-X. Gao, and F.-S. Han, Chem.
Eur. J. 2010, 16, 4991; (h) H. Chen, Z. Huang, X. Hu, G. Tang,
P. Xu, Y. Zhao, and C.-H. Cheng, J. Org. Chem. 2011, 76, 2338;
(i) C. Shi, and C. C. Aldrich, Org. Lett. 2010, 12, 2286; (j) V.
Percec, J.-Y. Bae, and D. H. Hill, J. Org. Chem. 1995, 60, 1060;
(k) N. Zhang, D. J. Hoffman, N. Gutsche, J. Gupta, and V.
Percec, J. Org. Chem. 2012, 77, 5956; (l) G.-J. Chen, and F.-S.
Han, Eur. J. Org. Chem. 2012, 3575; (m) X.-J. Li, J.-L. Zhang, Y.
Geng, and Z. Jin, J. Org. Chem. 2013, 78, 5078.
Ar2
C4
C2
CuI OZ
I
S
Ar2
Cu Cu
C3
Cs2S2
S
Cs2CO3
S
S
Ar2
Cu
Cu
CuII
CuII
Ar2
S
S8
Ar2 B(OH)2
Scheme 2. A plausible mechanism for the C-O bond activation
5
6
(a) B. M. Rosen, K. W. Quasdorf, D. A. Wilson, N. Zhang, A.-
M. Resmerita, N. K. Garg, and V. Percec, Chem. Rev. 2011,
111, 1346; (b) J. Yamaguchi, K. Muto, and K. Itami, Eur. J.
Org. Chem. 2013, 2013, 19; (c) D.-G. Yu, B.-J. Li, and Z.-J. Shi,
Acc. Chem. Res. 2010, 43, 1486; (d) M. Tobisu, and N.
Chatani, Top. Organomet. Chem. 2013, 44, 35.
reaction
Conclusions
In conclusion, we have developed a new Pd/Cu dual-metal
catalytic system for the synthesis of unsymmetrical diaryl
sulfides by the reaction of free-phenols and phenylboronic
acids in the presence of S8 at room temperature via C–O bond
activation. Significant advantages of the introduced system are
as follows: (i) one-pot odorless synthesis approach, which
offers the way more straightforward and practical; and (ii) use
of cheap, commercially available, easy-to-handle and
chemically stable starting substances, and catalysts. More
applications are under development regarding the introduced
system.
C. Shen, P. Zhang, Q. Sun, S. Bai, T.S.A. Hor, and X. Liu, Chem.
Soc. Rev., 2015, 44, 291.
7
8
M. Kosugi, T. Shimizu, and T. Migita, Chem. Lett. 1978, 13.
Some selected papers; (a) M. Murata, and S.L. Buchwald,
Tetrahedron let. 2004, 60, 7397; (b) T. Itoh, and T. Mase,
Org. Lett, 2004, 6, 4587; (c) M.A. Fernandez-Rodreguez, Q.
Shen, and J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 2180;
(d) M. Kuhn, F. C. Falk, and J. Paradies, Org. Lett., 2011, 13,
4100; (e) L. Wang, W. Y. Zhou, S. C. Chen, M. Y. He, and Q.
Chen, Adv. Synth. Catal., 2012, 354, 839; (f) N. Park, K. Park,
M. Jang, and S. Lee, J. Org. Chem., 2011, 76, 4371; (g) Y. Li,
C. Nie, H. Wang, X. Li, F. Verpoort, and C. Duan, European J.
Org. Chem., 2011, 2011, 7331.
Some selected papers; (a) H.-J. Xu, Y.-Q. Zhao, T. Feng, and
Y.-S. Feng, J. Org. Chem. 2012, 77, 2878; (b) C.-K. Chen, Y.-W.
Chen, C.-H. Lin, H.P.C. Lin, and F. Lee, Chem. Commun. 2010,
46, 282; (c) V. P. Reddy, A. V. Kumar, K. Swapna, and K. R.
Rao, Org. Lett. 2009, 11, 1697; (d) N. Iranpoor, H.
Firouzabadi, and A. Rostami, Appl. Organometal. Chem.
Conflicts of interest
There are no conflicts to declare.
9
Acknowledgments
We thank K. N. Toosi University of Technology and Iran
National Science Foundation (INSF). This research was
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins