ChemComm
Communication
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Scheme 2 Possible reaction pathways.
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oxidation of aryl sulphonyl hydrazide A with I2 affords B, which then
reacts with TsOH forming intermediate C and TsOI. Then, inter-
mediate C undergoes a self-dehydration reaction catalysed by TsOH,
11 F.-L. Yang and S.-K. Tian, Angew. Chem., Int. Ed., 2013, 52, 4929.
thus eliminating two molecules of water to afford intermediate F. G 12 N. Singh, R. Singh, D. S. Raghuvanshi and K. N. Singh, Org. Lett.,
2013, 15, 5874.
is obtained by eliminating one molecule of nitrogen from F. Finally,
the thiodiazonium species F or sulphenyl tosylate G is attacked by
13 F.-L. Yang, F.-X. Wang, T.-T. Wang, Y.-J. Wang and S.-K. Tian, Chem.
Commun., 2014, 50, 2111.
14 R. Singh, D. S. Raghuvanshi and K. N. Singh, Org. Lett., 2013, 15, 4202.
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the enol form of the pyrazolone to give the product. In the first and
second steps, I2 is converted to HI and TsOI that react with each
other to regenerate I2 and TsOH. Compared to that in Tian’s
protocol, the lifetime of the highly reactive thiodiazonium tosylate
is longer than that of thiodiazonium iodide. Moreover, the sulphenyl
tosylate is more reactive than sulphenyl iodide.21
In conclusion, we have developed an efficient I2-catalysed
and TsOH-promoted cross-coupling reaction of pyrazolones with
aryl sulphonyl hydrazides through direct C–H functionalization
to synthesize the corresponding aryl pyrazolone thioethers. This
study demonstrated that TsOH could facilitate this reaction by
enabling the decomposition of sulphonyl hydrazides in the
presence of 1 to 5 mol% of I2. Moreover, this study further
broadened the application of sulphonyl hydrazides as the emerging
electrophilic sulphenylation reagents in organic synthesis.
The project was supported by NSFC (Grant No. 21202119,
21202118 and 21102102) and the Scientific Research Foundation
of Tianjin Normal University (No. 5RL110).
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