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ChemComm
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DOI: 10.1039/C6CC10303K
Journal Name
COMMUNICATION
under the moderate condition. The results of deuterium
labeling study and in situ ESI-MS experiments indicate that
that the catalytic reaction probably through a Fe(II)/Fe(III)
catalytic cycle.
Notes
General procedure for preparation of 3 and 5
A mixture of phenyl-methanethiol 1a (0.3 mmol, 37.2 mg), 2-Iodo-
phenylamine 2a (0.3 mmol, 65.7 mg), Fe(OAc)2 (5 mol%, 8.7 mg), 2-
(2-Dimethylamino-vinyl)-inden-1-one L5 (5 mol%, 10.0 mg) and
Cs2CO3 (2 equiv, 195.6 mg) in DMSO (4 mL) was stirred under a N2
atmosphere. After the reaction mixture was stirred at 100 °C for 24
h, it was allowed to cool to ambient temperature. Then the mixture
was quenched with saturated salt water (10 mL), and the solution
was extracted with ethyl acetate (3 × 10 mL). The organic layers
were combined and dried by sodium sulfate and concentrated in
vacuo. The pure product 2-Phenyl-benzothiazole 5a (54.4 mg, 86%
yield) was obtained by flash column chromatography on silica gel.
Scheme 2. The in suit ESI-MS spectras of Fe(II)-catalyzed sulfur directed C-H
amination/C-S cross coupling.
Based on the above results, the reaction mechanism was
proposed (Scheme 4). After the coordination of Fe(OAc)2 with L5,
the corresponding intermediate 7 was generated.9 Next, a Fe(III)
intermediate 8 was formed by the oxidative addition of 7 with 2-
Acknowledgement
haloaniline. Next, 8 reacted with phenylmethanethiol produced This research was supported by the Natural Science
intermediate 9 by ligands exchange step. Subsequently, 9 afforded Foundation of Zhejiang Province (No. LQ15B020004), Natural
the key intermediate 10 by an intermolecular oxidative addition. Science Foundation of ZA
Finally, 10 furnished the desired products 3 through reductive
&FU (No. 04251700011).
elimination step, and meanwhile concomitantly generated the
References
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Fe(OAc)2
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H
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9
Scheme 3. Proposed mechanism.
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Conclusions
In conclusion, we have developed a Fe(II)-catalyzed sulfur
directed C(sp3)-H bonds amination/C-S cross coupling reaction.
The reaction was with high tolerance of functional groups
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J. Name., 2013, 00, 1-3 | 3
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