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Scheme 3 Substrate scope for the deacetylative arylation of aryl iodide 1 with
b-keto esters and amides 2. Reaction conditions: 1 (1.0 mmol), 2 (3.0 mmol), CuI
(10 mol%), K3PO4 (3.0 equiv.), alcohol (3.0 mmol) in 4 mL of DMSO in N2 at 80 1C
for 20 h, isolated yields; aMeOH was used, GC yield 90%; bnBuOH was used; cEtOH
was used, GC yield 79%; when tBuOH was used, only trace yield; dBnOH was used;
eEtOH was used; when CyOH was used, only 13% yield; fEtOH was used.
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In conclusion, we have developed a novel method of alcohol-
assisted copper-catalyzed highly selective deacetylative a-arylation
of b-keto esters and amides, which illustrated an efficient example
of achieving a-aryl esters and amides under mild conditions.
Assisted by the crucial alcohol, both selectivity and conversion
could be enhanced satisfactorily. From the synthetic point of view,
this arylation protocol is general and practical, representing a
simple way to produce a-arylated carbonyl compounds from basic
starting materials at low cost. Further mechanistic studies on this
alcohol-assisted deacetylative arylation transformation are currently
underway in our laboratory.
This work was supported by the 973 Program (2012CB725302),
the National Natural Science Foundation of China (21025206 and
21272180). We are also grateful for the support from the Program
for Changjiang Scholars and Innovative Research Team in
University (IRT1030).
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c
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