Journal of the American Chemical Society
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Kojima, R. W.; Kaner R. B.; Diaconescu, P. L. Angew. Chem., Int.
up experiment. For example, the hydroxylation of 1ꢀ(3ꢀ
chlorophenyl)ꢀethanone on a 20 mmol scale completed in 24 h
by using only 2 mol % catalyst and ligand (Scheme 1), while a
complete conversion was observed in 12 h when the hydroxꢀ
ylation of 3ꢀbromoꢀ1ꢀiodobenzene was run on a 20 mmol scale.
These additional advantages make the present method more atꢀ
tractive for largeꢀvolume production of phenols.
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Huang, C.ꢀW.; Chern, J.ꢀW. Org. Lett. 2012, 14, 3688ꢀ3691. (g)
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(5) For selected references on Cuꢀcatalyzed hydroxylation of (hetꢀ
ero)aryl halides, see: (a) Tlili, A.; Xia, N.; Monnier, F.; Taillefer, M.
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Scheme 1. Scaling up the hydroxylation reaction
In conclusion, we have demonstrated that N,N’ꢀbis(4ꢀhydroxyꢀ
2,6ꢀdimethylphenyl)oxalamide (BHMPO) is a superior ligand
for promoting Cuꢀcatalyzed hydroxylation of (hetero)aryl halꢀ
ides, which not only enables the hydroxylation of various (hetꢀ
ero)aryl chlorides, but also allows the much more facile forꢀ
mation of phenols and hydroxylated heteroarenes from (hetꢀ
ero)aryl bromides and iodides comparing to previous methods.
The hydroxylation features a broad substrate scope, the low
costs of both catalyst and ligand, as well as mild reaction conꢀ
ditions, which should be applicable in organic synthesis.
(6) For some synthetic applications of metalꢀcatalyzed hydroxylaꢀ
tion of (hetero)aryl halides, see: (a) Xu, C.; Zhang, Y.ꢀP.; Wang, Z.ꢀ
Q.; Fu, W.ꢀJ.; Hao, X.ꢀQ.; Xu, Y.; Ji, B.ꢀM. Chem. Commun. 2010, 46,
6852ꢀ6854. (b) Štefko, M.; Hocek, M. Synthesis 2010, 4199ꢀ4206. (c)
Ni, F.; Li, J. Synthesis 2012, 44, 3598ꢀ3602. (d) Ritter, J. C.
US7339076 (2008).
ASSOCIATED CONTENT
Supporting Information.
Experimental procedures and compound characterization. This
material is available free of charge via the Internet at
(7) For some recent studies on synthesis of phenols by using other
methods, see: (a) Yamada, M.; Karlin, K. D.; Fukuzumi, S. Chem. Sci.
2016, 7, 2856ꢀ2863. (b) Fier, P. S.; Maloney, K. M. Org. Lett. 2016,
18, 2244ꢀ2247. (c) Shoji, O.; Kunimatsu, T.; Kawakami, N.;
Watanabe,Y. Angew. Chem., Int. Ed. 2013, 52, 6606ꢀ6610. (d) Yan,
Y.; Feng, P.; Zheng, Q.ꢀZ.; Liang, Y.ꢀF.; Lu, J.ꢀF.; Cui, Y.; Jiao, N.
Angew. Chem., Int. Ed. 2013, 52, 5827ꢀ5831. (e) Choy, P. Y.; Kwong,
F. Y. Org. Lett. 2013, 15, 270ꢀ273. (f) Zou, Y.ꢀQ.; Chen, J.ꢀR.; Liu,
X.ꢀP.; Lu, L.ꢀQ.; Davis, R. L.; Jørgensen, K. A.; Xiao, W.ꢀJ. Angew.
Chem., Int. Ed. 2012, 51, 784ꢀ788. (g) Sergeev, A. G.; Webb, J. D.;
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P.; Ma, X.; Nguyen, K.; Zhao, Y. Angew. Chem., Int. Ed. 2012, 51,
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AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
The authors are grateful to Chinese Academy of Sciences (supꢀ
ported by the Strategic Priority Research Program, grant
XDB20020200 & QYZDJꢀSSWꢀSLH029) and the National Natuꢀ
ral Science Foundation of China (grant 21132008) for their finanꢀ
cial support.
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