Jayeeta Bhattacharjee et al.
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Scheme 2. Most plausible mechanism for the catalytic
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catalyst 3.
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4. Conclusions
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In summary, we have presented the highly chemo-
selective catalytic addition of N–H bonds from vari-
ous aromatic amines to carbodiimides and isocyanate
using a zinc pre-catalyst supported by N-(aryl)imino-
acenapthenone ligand. The zinc complex 3 was proved
to be efficient pre-catalyst for the conversion of aro-
matic amines to the corresponding guanidines via
guanylation reaction with carbodiimides at elevated
temperature in 55–95% yield. Complex 3 was also a
potent catalyst for the conversion of isocyanate to cor-
responding urea in excellent yield when amines were
reacted with isocyanate at room temperature. A possi-
ble mechanism involving five coordinated zinc interme-
diate is proposed for the guanylation reaction.
Supplementary Information (SI)
1
The H and 13C NMR spectral data for guanidine (B-
K) and urea derivatives (M-O) are given in the Sup-
1
porting Information. The H and 13C NMR spectra
for guanidine and urea derivatives B-P are given in
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and Sanchez Agullo P 1994 Tetrahedron: Asymmetry 5
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1992 J. Org. Chem. 57 2497
7. For general reviews on guanylating agents, see: (a)
Katritzky A R and Rogovoy B V 2005 ARKIVOC 4 49; (b)
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315
Acknowledgements
This work was supported by Science and Engineer-
ing Research Board (SERB), Department of Sci-
ence and Technology (DST), India under project no.
(SB/S1/IC/045/2013). The instrumental facilities were
provided by the Indian Institute of Technology Hyder-
abad (IITH). J. B. thanks UGC, India for her PhD
fellowship.