10.1002/anie.201813148
Angewandte Chemie International Edition
COMMUNICATION
dioxane (0.3 mL, 1.0 M), and water (54 µL, 3.0 mmol) were placed in a
25 mL Schlenk reactor and stirred for 10 min at room temperature.
Afterward, styrene (2a, 103 µL, 0.9 mmol) was added, and the reaction
mixture was allowed to stir at 100 °C for 23 h. Then, the mixture was
cooled to room temperature. This resultant mixture was subjected to
reduce pressure on the rotary to remove the solvent, and the obtained
residue was purified through silica gel column chromatography
(petroleum ether/ethyl acetate = 5:1) to obtain pure 3aa as colourless oil
(60.1 mg, 84%).
mechanism involves two catalytic cycles starting from
[LnCu(I)Sn]+ A and ArCOOAg C, correspondingly, which are
generated in situ from the precatalysts Cu(MeCN)4PF6 and
AgSbF6. The reaction of catalytic species [LnCu(I)Sn]+ A with
cinnamyl alcohol (1a) in the presence of a Brønsted acid would
occur to generate an intermediate η3-allyl copper(III) carboxylate
B. Meanwhile, the coordination of catalytic species ArCOOAg C
to C=C double bond of styrene (2a) would occur to generate an
intermediate D, which would subsequently undergo hydration
reaction to afford an intermediate organic silver E.
Intermolecular hydrogen-bond interaction between intermediates
Acknowledgements
B
and
E
would produce intermediate F. Intramolecular
to
nucleophilic substitution-like reaction would occur in
F
The authors are grateful to the National Natural Science
Foundation of China (No. 21573032 and 21602026), the China
Postdoctoral Science Foundation (No. 2016M590226), and the
Fundamental Research Funds for the Central Universities (No.
DUT18RC(4)043) for their financial support.
generate an intermediate G and regenerate catalytic species
ArCOOAg C. Ligand exchange reaction of G with MeCN and/or
solvent would finally occur to produce the desired product 3aa
and regenerate catalytic species [LnCu(I)Sn]+ A, which could be
stabilized by phosphine ligands and coordinating solvents.[18]
Keywords: carbohydroxylation • cooperative catalysis • copper
• silver • Brønsted acid • arylalkene
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Scheme
carbohydroxylation of styrenes.
2.
Proposed
mechanism
for
the
catalytic
allylative
In summary, we developed
functionalization reaction to convert arylalkenes into valuable
4,5-unsaturated alcohols. The direct allylative
a
new type of olefin
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carbohydroxylation of arylalkenes with allylic alcohols proceeded
through cooperative catalysis of Cu, Ag, and Brønsted acid
under mild conditions to provide 4,5-unsaturated alcohols in
satisfactory to good yields. Synthetically useful functional groups,
such as Cl, Br, carbonyl, and chloromethyl, remained intact
during the direct carbohydroxylation of arylalkenes. Further
studies on the asymmetric direct allylative carbohydroxylation of
arylalkenes by using chiral phosphine ligands and chiral
phosphoric acids are ongoing.
[5]
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Experimental Section
The 3aa preparation is given here as representative method.
Cu(CH3CN)4PF6 (5 mol%, 5.6 mg), AgSbF6 (0.06 mmol, 20.6 mg), rac-
BINAP (6 mol%, 11.0 mg), cinnamyl alcohol (1a, 0.3 mmol, 40.2 mg), 4-
NO2BzOH (0.06 mmol, 10.0 mg), acetonitrile (31.3 µL, 0.6 mmol), 1,4-
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