G Model
CCLET 3635 1–4
S.-L. Yi et al. / Chinese Chemical Letters xxx (2016) xxx–xxx
3
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173
175
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178
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Scheme 1. Plausible mechanism of TBN-catalyzed aerobic oxidation of thiols to
disulfides.
183
(b) H. Firouzabadi, N. Iranpoor, A. Samadi, One-pot synthesis ofaryl alkyl 184
thioethers and diaryl disulfides using carbon disulfide as a sulfur surrogate in 185
the presence of diethylamine catalyzed by copper(I) iodide in polyethylene glycol 186
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
thiol substrates could be smoothly converted to corresponding
disulfides with excellent yields without any evidence for the
formation of sulfonic acids under mild conditions in short time. All
aromatic thiols were more active and provided better product
yields than those of heteroaromatic thiols and aliphatic thiols. The
steric effects and electronic effects in aromatic thiols did not play
important roles in the isolated yield of the desired products
(entries 2–12). In addition, oxidative coupling reaction using
thiosalicylic acid (1m) as the substrate successfully took place
under present catalytic conditions. What is more, heteroaromatic
thiols (1n–1r) also could be successfully converted into desired
products (2n–2r) (entries 13–18), although higher loading of TBN
was needed (entries 13–15 and 17). For 2-mercaptobenzimidazole
(1r), which was difficult to dissolve in most of solvents, the amount
of TBN needed to be increased to 30 mol% to complete the reaction
(entry 18). Finally, aliphatic thiols also could produce the target
products in moderate yields (entries 19 and 20).
According to the literature [30], a plausible reaction mechanism
for TBN-catalyzed aerobic oxidation of thiols to disulfides has been
proposed (Scheme 1). TBN releases NO under 50 8C, and then NO is
easily oxidized by oxygen to form NO2. NO2 reacts with NO to form
N2O3, which reacts with RSH to form unstable RSNO and
HNO2. RSSR get from the hemolytic cleavage of the sulfur-nitrogen
bond of the RSNO and then coupling of the resultant thiyl radicals.
(PEG200), Tetrahedron Lett. 55 (2014) 1212–1217.
187
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190
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53 (2012) 7028–7030.
194
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leading to aryl chalcogenides, Adv. Synth. Catal. 356 (2014) 749–752;
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200
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211
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system for the oxidation of alcohols, thiols and sulfides in the absence of solvent, 213
Chin. Chem. Lett. 19 (2008) 51–54.
214
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disulfides, Tetrahedron 67 (2011) 8895–8901.
216
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143
4. Conclusion
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disulfides, Tetrahedron Lett. 45 (2004) 8489–8491.
[21] S. Patel, B.K. Mishra, Cetyltrimethylammonium dichromate: a mild oxidant for 227
coupling amines and thiols, Tetrahedron Lett. 45 (2004) 1371–1372.
222
224
226
228
144
145
146
147
148
149
In conclusion, we have successfully developed a mild and
convenient catalytic approach for the oxidative coupling of thiols
to the corresponding disulfides. The significant features of our
protocol are metal-free, atom efficiency, using of molecular oxygen
as the terminal green oxidant. Furthermore, the isolation of the
products is remarkably easy.
[22] G. Joshi, S. Bhadra, S. Ghosh, et al., Making full use of the oxidizing equivalents in 229
bromate in the selective oxidation of thiols, sulfides, and benzylic/secondary 230
alcohols into disulfides, sulfoxides, and aldehydes/ketones, Ind. Eng. Chem. Res. 231
150
Acknowledgment
49 (2010) 1236–1241.
232
[23] N. Iranpoor, H. Firouzabadi, A.R. Pourali, Dinitrogen tetroxide supported on 233
polyvinylpyrrolidone (PVP–N2O4): a new nitrosating and coupling agent for 234
151 Q2
This work was financially supported by the National Natural
Science Foundation of China (nos. 21376224, 21206147).
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(2002) 5179–5184.
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a selective oxidant for sulfides and disulfides, Tetrahedron 58 235
152
236
238
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Please cite this article in press as: S.-L. Yi, et al., An efficient and convenient method for the preparation of disulfides from thiols using