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Organic & Biomolecular Chemistry
DOI: 10.1039/C7OB02012K
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proper in the system; finally, the reaction presents higher
yields and total conversion rates. Importantly, our novel
protocol opens a new door to synthesize 2ꢀoxoꢀacetamidine
derivatives, which makes the obtained αꢀamino carbonyl
compounds more valuable with some special complex
bioactivities and drug activity.
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60
65
70
75
80
5
Experimental
General Information
Chemicals were either purchased or purified by standard
10 techniques. All reactions were carried out under a nitrogen
atmosphere unless otherwise noted. Column chromatography
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1
separations were performed on silica gel (200−300 mesh). H
and 13C NMR spectra were recorded on a Varian Inovaꢀ400
spectrometer (400MHz for 1H, 100 MHz for 13C). NMR
15 chemical shifts were measured relative to the signals of
residual CHCl3 (δH 7.26 ppm and δC 77.16 ppm) or DMSOꢀd6
(δH 2.50 ppm) and DMSOꢀd6 (δC 39.520 ppm). LRMS was
performed on a GCꢀMS instrument and HRMS was measured
on an electrospray ionization (EI) apparatus using timeꢀofꢀ
20 flight (TOF) mass spectrometry. Melting points are
uncorrected.
General Procedure for the Synthesis of Product 3aa
To a flameꢀdried Roundꢀbottomed flask with a magnetic
stirring bar were charged 1a (63.3 mg, 0.3 mmol), aniline 2a
25 (55.8 mg, 0.6 mmol), Cu(OAc)2·H2O (3 mg, 5 mol%), TBHP
(38.5 mg, 0.3 mmol) in DCE (2 mL) under nitrogen
atmosphere. The reaction mixture was stirred at 60 °C until
complete consumption of the starting material as detected by
TLC or GCꢀMS analysis. After the reaction was finished, the
30 reaction mixture was washed with brine. The aqueous phase
was reꢀextracted with ethyl acetate. The combined organic
extracts were dried over Na2SO4 and concentrated in vacuum,
and the resulting residue was purified by silica gel column
chromatography (petroleum ether/ethyl acetate = 8:1, V/V) to
35 afford the desired product in 91% yield (82 mg) as a yellow
solid.
85
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Acknowledgements
We are grateful for financial support from the National
Natural Science Foundation of China (Nos. 21502049 and
40 51573040), and the Planned Science and Technology Project
of Hunan Province, China (No. 2015WK3003).
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Notes and references
a
State Key Laboratory of Chemo/Biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan
45 University, Changsha, 410082, P. R. China.
b College of Chemistry and Chemical Engineering, Central South
University, Changsha 410083, P. R. China.
c School of Chemistry and Chemical Engineering, Hunan Institute
of Engineering, Xiangtan, 411104, P. R. China.
50 eꢀmail: jnxiang@hnu.edu.cn; eꢀmail: yiniannian@hnu.edu.cn
† Electronic Supplementary Information (ESI) available: See
DOI: 10.1039/b000000x/
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