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Journal Name
Organic & Biomolecular Chemistry
DOI: 10.1039/C5OB00135H
The intermolecular deuterium kinetic isotope effect (KIE) of the
Cu(OAc)2ꢀcatalyzed electrophilic amination was then measured in a
competitive coupling of an equimolar mixture of quinoline and 2ꢀd1ꢀ
quinoline Nꢀoxides with O-benzoyl hydroxylamines (Scheme 2).
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1
The KIE was KH/KD = 1.1, as observed via H NMR analysis of the
,
residual material mixture. The data implicated the CꢀH bond
activation in quinoline Nꢀoxide was not likely involved in the rateꢀ
limiting step.
,
,
,
,
,
,
,
,
,
,
6900; (c) J. A. Souto, P. Becker, Á. Iglesias, K. Muñiz, J. Am. Chem.
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Scheme 3. Plausible Mechanism of Electrophilic Amination
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Although the detailed mechanism of Cu(II)ꢀcatalyzed couplings of
arenes and hydroxylamine derivatives remains unclear, a plausible
catalytic cycle for the electrophilic amination was proposed on the
basis of our experimental results and related literature (Scheme
3).[14] The initial reduction of Cu(II) into Cu(I) and complexation
with solvents produced the catalytically active species A. The
metallization of Quinoline Nꢀoxide with species A then generated
arylcopper B, which was added to Oꢀbenzoyl hydroxylamine to form
the crucial intermediate C. Subsequently, the species C underwent a
reductive elimination to release Cu(I)OBz and the final product. The
final ligand exchange with the solvent regenerated the starting
catalytic species A to restart the catalytic cycle.
In conclusion, we developed a Cu(OAc)2ꢀcatalyzed electrophilic
amination of quinolineꢀNꢀoxides with R2N(+) synthons provided by
Oꢀbenzoyl hydroxylamines. This development provides a new
strategy for the synthesis of 2ꢀaminoquinoline compounds via aryl
CꢀH bond activation and electrophilic amination.
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We gratefully acknowledge the National Natural Science
foundation of China (No. 21102005) for financial support of this
work.
Notes and references
a College of Chemistry and Chemical Engineering Anyang Normal University
Anyang, 455000 P. R. China Fax: (+86)ꢀ372ꢀ2900040; Eꢀmail:
ligang@aynu.edu.cn; hkwu@aynu.edu.cn
b School of Biomedical Sciences, Huaqiao University, Xiamen, 361021 P. R.
China
1For recent selected examples of CꢀH bond functionalization, see: (a) J.ꢀ
Q. Yu, Z.ꢀJ. Shi, CꢀH Activation; SpringerꢀVerlag: Berlin Heidelberg,
2010; (b) M. P. Doyle, K. I. Goldberg, Acc. Chem. Res. 2012, 45
(c) T. Bruckl, R. D. Baxter, Y. Ishihara, P. S. Baran, Acc. Chem. Res.
2012, 45 826; (d) P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem.
, 777;
,
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