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RSC Advances
DOI: 10.1039/C6RA01295G
COMMUNICATION
3%. Based on these results, we proposed a plausible pathway
Journal Name
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for the reaction, which was shown in Scheme 4.
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Scheme 5 Investigations into the reaction mechanism
When we performed the reaction under the optimum
condition in the presence of 4.0 equiv. radical scavenger
6
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2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO), the title
compound was obtained in 21% because the reactant 2-
bromo-benzenethiol (2a) was decomposed by TEMPO (Scheme
5). And the intermediate 4a was also employed under the
optimum condition in the presence of 4.0 equiv. TEMPO, the
product 3a was obtained in 79% yield. The results indicated
the reaction might be completed without a radical pathway. To
investigate whether a benzyne intermediate was formed
during coupling progress, 3-bromo-benzenethiol was
employed as the substrate instead of 2-bromo-benzenethio
under the optimum condition (Scheme 5). And the
corresponding product 3a was not observed.
P. Chen, F. H. Xiao, G. J. Deng, RSC Adv., 2013, 3, 18605.
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In summary,
a potassium carbonate-mediated tandem
intermolecular C-S and intramolecular C-N coupling reaction
was developed for the construction of pharmacological and
clinical useful phenothiazine derivatives for the first time. This
transition-metal-free and ligand-free protocol was economic
1
32, 16737; (d) E. Shirakawa, K. Itoh, T. Higashino and T.
Hayashi, J. Am. Chem. Soc., 2010, 132, 15537.
0 I. Thomé and C. Bolm, Org. Lett., 2012, 14, 1892.
efficiency and environment benign. The starting materials 11 (a) X. Y. Liu and S. L. Zhang, Synlett., 2011,
2, 268; (b) X. Y. Liu
were readily available and the condition was simple. And the
product could be obtained in good yield when large scale
reaction was conducted.
and S. L. Zhang, Synlett., 2011,
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Taillefer, ChemCatChem, 2009, , 504-509.
CO
8, 1137.
1
,
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7
0
We would like to gratefully acknowledge financial support
1
from the A Project Funded by the Priority Academic Program 13 The main transition-metal impurities of K
2
3
had been also
analyzed by ICP-MS by Shanghai Institute of Measurement
and Testing Technology (SIMT).
for the Development of Jiangsu Higher Education Institutions,
The Project of Scientific and Technologic Infrastructure of
Suzhou (No. SZS201207) and the National Natural Science
Foundation of China (No. 21072143).
Fe Co
mg/kg mg/kg
Ni
Cu
Pd
mg/kg mg/kg mg/kg
K
2
CO
3
< 1
< 1
< 1
< 1
< 1
Notes and references
‡
Key Laboratory of Organic Synthesis of Jiangsu Province,
College of Chemistry, Chemical Engineering and Materials
Science, Soochow University, Suzhou 215123, P. R. China.
E-mail: zhangsl@suda.edu.cn
Electronic supplementary information (ESI) available:
Experimental procedures, characterization and spectral data of
the products. See DOI: 10.1039/b000000x/
4
| J. Name., 2012, 00, 1-3
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