Green Chemistry
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DOI: 10.1039/C6GC03142K
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On the basis of the aforementioned experimental results and
the previous reports,14g,16,17 a possible reaction pathway was
proposed and depicted in scheme 6. Initially, thermally promoted
homolytic cleavage of the radical initiator TBHP produces a tertꢀ
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t
butoxy radical BuO·, which converts to the methyl radical by
releasing 1 equiv of acetone in the presence of Cu.17c,18
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intermediate 6 which can isomerize to 7 to form copper
intermediate 8 in the presence of the Cu(II). Finally, the methyl
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radical reduces the Cu(II) intermediate
8 to produce Sꢀ
methylation compound 3a and regenerate Cu(I), which is
oxidized to Cu(II) for further reactions.
Conclusions
A copperꢀcatalyzed Sꢀmethylation of sulfonyl hydrazides with
TBHP was efficiently developed, affording a variety of methyl
sulfones with good to excellent yields. This new Sꢀmethylation
can be carried out in water under environmentally benign
conditions without any ligand or additive. And the copper
catalystꢀinꢀwater can be recovered by a simple phase separation
and this catalyst in water can be recycled for several times
without obvious loss of catalytic activity. Also, the byꢀproducts
were nitrogen, acetone and water, no any pollution on the
environment. What’s more, the reaction has a broad scope of the
reaction substrates, a variety of functional groups can perform
well in the reaction conditions. Ongoing research including
further mechanistic details, expanding the substrate scope and
applications in organic synthesis are currently underway.
Experimental
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A mixture of sulfonyl hydrazides (0.20 mmol), TBHP (0.40
mmol) and Cu(OTf)2 (20 mol %) in water (1 mL) was put into a
schlenk at 120 °C under magnetic stirring for 12 h under nitrogen.
After the reaction was finished, the mixture was extracted with
EtOAc (3 × 5 mL) and then the combined organic extracts were
washed with brine (10 mL), dried over sodium sulfate, and
filtered. The solvent was removed under reduced pressure and the
residue was purified by flash column chromatography
(hexane/ethyl acetate = 3:1) to give compound 3.
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Acknowledgements
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We are grateful to the National Nature Science Foundation of
China (21272222, 91213303, 21172205, J1030412).
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a Hefei National Laboratory for Physical Sciences at Microscale, CAS
Key Laboratory of Soft Matter Chemistry and Department of Chemistry &
Collaborative Innovation Center of Suzhou Nano Science and
Technology, University of Science and Technology of China, Hefei,
230026, P. R. China. Fax: (+86) 551ꢀ360ꢀ3185; Eꢀmail:
† Electronic Supplementary Information (ESI) available: Experimental
details and characterization of products. See DOI: 10.1039/b000000x/
‡ These authors contributed equally to this work.
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