Communication
Green Chemistry
21
oxidized by DMSO to DMS·Br2 which would coordinate with
DMSO to form [(DMSO)nBr+]Br− (n = 1 or 2) according to
Yoshida’s report.16 The electrophilic addition occurred
between Br+ and alkene 3 to form bromonium A. Further
nucleophilic attack of DMSO to A afforded the alkoxysulfon-
ium ion B which quickly decomposed to produce bromo-
hydrin 2.4g
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Conclusions
In conclusion, we have demonstrated a new application of
DMSO in organic synthesis. To the best of our knowledge, this
is the first direct transformation of secondary bromides to
highly value-added bromohydrins. The very cheap and
common DMSO gives its sensational performance as the key
point of this reaction. On the basis of the mechanism, the
hydroxybromination of styrenes was also disclosed in high
efficiency with aqueous HBr and DMSO. Although water and
ethyl acetate were used in the work-up process, the present
protocol with DMSO as the combined role of a solvent,
oxidant, and oxygen source is simpler and more practical than
the reported methods employing indispensable reagents of a
solvent, an acid, an oxygen source, and an oxidant.14 Simple
conditions, low-cost and readily available reagents, and easy
operability made the present preparation of bromohydrins
surpass the reported approaches. This discovery may open an
avenue for the further exploration and utilization of DMSO in
organic synthesis. Further discovery of DMSO as an oxidant or
an oxygen source is ongoing in our laboratory.
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Acknowledgements
Financial support from National Basic Research Program of
China (973 Program) (grant no. 2015CB856600) and National
Natural Science Foundation of China (no. 21325206,
21172006) and National Young Top-notch Talent Support
Program are greatly appreciated. We thank Xiang Sun in this
group for reproducing the results of 4e and 5e.
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Green Chem.
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