10.1002/chem.201604098
Chemistry - A European Journal
FULL PAPER
Johnson, D. R. Sliskovic, B. D. Roth in Contemporary drug synthesis;
John Wiley & Sons: 2004. c) J. Heeres, L. J. J. Backx, J. Van Cutsem,
J. Med. Chem 1984, 27, 894-900. For general reviews see: d) G. M.
Brooke, J. Fluor. Chem. 1997, 86, 1-76. e) F. Terrier in Modern
nucleophilic aromatic substitution; Wiley-VCH, Weinheim, 2013.
Qutes from leading text books in organic chemistry: a) “Without
electron-attracting groups present, nucleophilic aromatic substitution
occurs only under extreme reaction condtions“ F. A. Carey, R. J.
Sundberg in Advanced Organic Chemistry: Part A: Structure and
Mechanisms; 4th ed. Springer Science and Business Media, New York,
2000. b) “To summarize: Any anion-stabilizing (electron-withdrawing)
group ortho or para to a potential leaving group can be used to make
nucleophilic aromatic substitution possible.” J. Clayden, N. Greeves, S.
Warren, P. Wothers in Organic Chemistry; Oxford University Press,
New York, 2001.
Dec 4, 2014. d) Y. Mao, L. Jiang, T. Chen, H. He, G. Liu, H. Wang,
Synthesis 2015, 47, 1387-1389.
[9]
[10] a) F. Diness, D. P. Fairlie, Angew. Chem. Int. Ed. 2012, 51, 8012-8016.
b) F. Diness, M. Begtrup, Org. Lett. 2014, 16, 3130-3133. c) X. Kong, H.
Zhang, Y. Xiao, C. Cao, Y. Shi, G. Pang, RSC Adv. 2015, 5, 7035-7048.
[11] a) H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119-2183. b) R. D.
Chambers, P. A. Martin, G. Sandford, D. L. Williams, J. Fluor. Chem.
2008, 129, 998-1002. c) M. Giese, M. Albrecht, K. Rissanen, Chem.
Rev. 2015. d) Z. Wu, R. Glaser, J. Am. Chem. Soc. 2004, 126, 10632-
10639. e) W. Qian, H. Wang, M. D. Bartberger, J. Am. Chem. Soc.
2015, 137, 12261-12268.
[12] A patent application covering this work has been filed by the authors
(Danish patent application no. PA 2016 70066).
[13] For related studies see: a) Y. Ito, K. Ohmori, K. Suzuki, Angew. Chem.
Int. Ed. 2014, 53, 10129 –10133; b) C. L. Cheong, B. J. Wakefield, J.
Chem. Perkin Trans. 1 1998, 12, 3301-3305.
[14] R. Bolton, J. P. B. Sandall, J. Fluor. Chem. 1982, 21, 459-467.
[15] For
a
overview
of
pKa
values
in
DMSO
see:
2016).
[16] a) C. Desmarets, R. Schneider, Y. Fort, J. Org. Chem. 2002, 67, 3029-
3036. b) N. Kataoka, Q. Shelby, J. P. Stambuli, J. F. Hartwig, J. Org.
Chem. 2002, 67, 5553-5566. c) B. U. Maes, K. T. Loones, S. Hostyn, G.
Diels, G. Rombouts, Tetrahedron 2004, 60, 11559-11564. d) S.
Urgaonkar, J. G. Verkade, J. Org. Chem. 2004, 69, 9135-9142. e) I. C.
Lerma, M. J. Cawley, F. G. Cloke, K. Arentsen, J. S. Scott, S. E.
Pearson, J. Hayler, S. Caddick, J. Organomet. Chem. 2005, 690, 5841-
5848. f) Q. Shen, T. Ogata, J. F. Hartwig, J. Am. Chem. Soc. 2008, 130,
6586-6596. g) M. Otsuka, K. Endo, T. Shibata, Chem. Comm. 2010, 46,
336-338. h) D. Guo, H. Huang, Y. Zhou, J. Xu, H. Jiang, K. Chen, H.
Liu, Green Chem. 2010, 12, 276-281. i) B. Lü, P. Li, C. Fu, L. Xue, Z.
Lin, S. Ma, Adv. Synt. Cat. 2011, 353, 100-112.
[17] a) G. Miao, P. Ye, L. Yu, C. M. Baldino, J. Org. Chem. 2005, 70, 2332-
2334. b) M. G. Andreu, A. Zapf, M. Beller, Chem. Comm. 2000, 2475-
2476.
[18] a) L. Wang, Z. X. Wang, Org. Lett. 2007, 9, 4335-4338. b) S. Saito, S.
Oh-tani, N. Miyaura, J. Org. Chem. 1997, 62, 8024-8030.
[19] For an example of related high temperature sealed tube reactions see:
X. Meng, Z. Cai, S. Xiao, W. Zhou, J. Fluor. Chem. 2013, 146, 70–75.
For examples of related transition metal catalysed reactions see
reference 14.
[20] B. Buettelmann, S. M. Ceccarelli, G. Jaeschke, S. Kolczewski, R. H. P.
Porter, E. Vieira, Preparation of pyridin-4-ylethynylimidazoles and-
pyrazoles as mGluR5a receptor antagonists. PCT Int. Appl. WO
2005118568, Dec 15, 2005. Chem. Abstr. 2005, 144, 51579.
[21] a) B. Bang-Andersen, T. Ruhland, M. Jørgensen, G. Smith, K.
Frederiksen, K. G. Jensen, H. Zhong, S. M. Nielsen, S. Hogg, A. Mørk,
J. Med. Chem. 2011, 54, 3206-3221. b) K. L. Christensen, Process for
the
manufacture
of
1-[2-(2,4-dimethyl-phenylsulfanyl)-phenyl]-
piperazine. PCT Int. Appl. WO 2013102573, Jul 11, 2013. c) B.
Zupancic, New process for the synthesis of 1-(2-((2,4-
dimethylphenyl)thio)phenyl)piperazine. PCT Int. Appl. WO 201419154,
This article is protected by copyright. All rights reserved.