Chemistry - A European Journal
10.1002/chem.201603041
COMMUNICATION
[a] Reaction conditions: 1 (0.2 mmol), 4 (0.6 mmol), H2O (0.5 mL), 45 oC, 5 h
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In conclusion, a simple procedure for difunctionalization of
alkenes has been developed, direct constructing various β-keto
sulfides and β-keto sulfones without any catalysts in water under
O2 atmosphere. Importantly, mild reaction conditions, purification
simplicity and high chemical selectivity are prominent
advantages for its practicability. Moreover, gram-scale synthesis
further demonstrates the potential application of the
methodology in chemical industry. Ongoing research, including
further mechanistic details and substrate scope, are currently
underway.
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Experimental Section
Typical procedure for the synthesis of 3a
To an oven-dried Schlenk tube equipped with a stir bar was
added p-toluenethiol (2a, 0.60 mmol), and a balloon filled with
dry oxygen was connected to the Schlenk tube through the side
arm and purged one time. Then, diethyl 1-phenylvinyl phosphate
(1a, 0.20 mmol), and H2O (0.5 mL) were successively injected
into the reaction tube with magnetic stirring. The reaction
mixture was allowed to stir vigorously at room temperature for 3
h. Thereafter, the mixture was extracted with ethyl acetate (x 4).
The combined organic layers were dried (Na2SO4) and
concentrated under reduced pressure. The resulting crude
product was separated on a silica gel column with petroleum
ether and ethyl acetate as eluent to afford the desired product.
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Acknowledgements
This work was supported by the 973 Program (2012CB725302),
the National Natural Science Foundation of China (21390400,
21520102003, 21272180, 21302148), the Hubei Province
Natural Science Foundation of China (2013CFA081), the
Research Fund for the Doctoral Program of Higher Education of
China (20120141130002), and the Ministry of Science and
Technology of China (2012YQ120060). The Program of
Introducing Talents of Discipline to Universities of China (111
Program) is also appreciated
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Keywords: catalyst-free • water • alkenes difunctionalization •
dioxygen activation • gram-scale synthesis
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