10.1002/ejoc.202001306
European Journal of Organic Chemistry
COMMUNICATION
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allylic alcohol (1) and sulfinic acid (2) may be the main path in
common aprotic organic media (such as 1,4-dioxane and
toluene) (Scheme 3, Path a). While a water-mediated and
substrate self-assisted activation of allylic alcohols via the
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cleavage of C-O bond affords the crucial π-allyl palladium 8,
meanwhile giving the nucleophilic sulfinate. Finally, a following
nucleophilic attack by sulfinate gives the target products 3 and
regenerates the palladium catalyst. Possibly owing to that it is
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may be the main binding species, and the reaction mainly
follows path b in aqueous media (path b). On the other hand, the
six member ring species 4 may be the main species, being in
charge of the activation of allylic alcohols in common aprotic
organic solvent (path a).13 These experimental results are also
consistent with the facts that the reaction could afford the target
product 3a with the highest yield in aqueous media, while the
target 3a could still be obtained with inferior yields in common
organic solvents (Table 1, runs 6-9).22
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Scheme 3. Possible reaction path way
In conclusion, we developed a mild, green and extra activator-
free dehydrative synthesis of allylic sulfones via Pd-catalyzed
allylic substitution of allylic alcohols with sulfinic acids in
aqueous media. This new method can tolerate various functional
groups such as MeO-, F-, Cl-, CN- etc. and can be easily scaled
up in gram scale in a nearly quantitative yield. Mechanism
studies suggested the formation of an eight-membered ring
complex from allylic alcohols, sulfinic acids and water via
hydrogen bonding may be crucial to the efficient activation of
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Acknowledgements
We thank the Foundation of Key Scientific and Technological
Project of Henan Province (192102310031),the Key Research
Programs in Universities of Henan Province (19B150018,
18A150049), the National Natural Science Foundation of China
(No.21803050, 21804117), the Nanhu Scholars Program for
Young Scholars of XYNU, the Young Core Instructor Program of
XYNU (2018GGJS—05) and Research and innovation projects
for college students (2019-DXS-026).
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Keywords: Allylic sulfones • Tsuji-Trost reaction • Hydrogen
bond activation • Dehydrative synthesis • Aqueous media
4
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