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Organic & Biomolecular Chemistry
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Journal Name
COMMUNICATION
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Chen, F. J.; Liao, G.; Li, X.; Wu, J.; Shi, B. F., Org. Lett., 2014, 16,
According to the above mechanistic investigations and our
previous work,53,54 a plausible mechanism is proposed for this
thiolation reaction. As shown in Scheme 2, the transformation
commences by the formation of the active Cu(I) species C by the
reaction of tBuONa and CuCl2. Then, a C-H activation process occurs
between species C and benzothiazole to afford the intermediate D,
which will further react with sulfur to give the desired product. Since
the EPR results suggested that the S3 is an active species in this
transformation, we guess it might plays a key role in the thiolation
process of D.
5644.
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6
7
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9
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Scheme 2. Plausible mechanism.
13 Gareau, Y.; Pellicelli, J.; Laliberté, S.; Gauvreau, D.,
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27 Chen, M.; Zheng, X.; Li, W.; He, J.; Lei, A. J. Am. Chem. Soc.
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In conclusion, a copper-catalyzed direct C-H bond thiolation of
electron-deficient arenes was demonstrated by utilizing elemental
sulfur as the thiolation agent. Various electron-deficient arenes were
proved to be suitable for this transformation. Preliminary
mechanistic studies indicated that this reaction underwent a radical
pathway, in which trisulfur radical anion (S3•-) might play a vital role.
Meanwhile, KIE experiments suggested that C-H bond cleavage was
not involved in the rate-determining step. According to the current
investigations, a plausible mechanism is proposed. More detailed
mechanism is currently under investigation in our laboratory and will
be reported in the near future.
This work was supported by the National Natural Science
Foundation of China (21390400, 21520102003, 21272180, 21302148,
21702150), the Hubei Province Natural Science Foundation of China
(2013CFA081), the Research Fund for the Doctoral Program of Higher
Education of China (20120141130002), and the Ministry of Science
and Technology of China (2012YQ120060), and China Postdoctoral
Science Foundation (BX201600114, 2016M602340). The Program of
Introducing Talents of Discipline to Universities of China (111 Pro-
gram) is also appreciated.
37 Chen, J.; WO2005086904, 2005
.
38 Zhang, C.; Wang, L.; Ge, Y.; Ju, X.; Chin. J. Org. Chem., 2007
,
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