4
Tetrahedron
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major and minor products. These results indicate that type of
metal salts was crucial for achieving selectivity.
In order to demonstrate synthetic utility of C as well as
N-arylated compounds, as intermediate we identified C-arylated
compound 3ama and N-arylated compound 4a. Compound 3ama
on treatment with CuI, in the presence on phenanthroline ligand,
lead C-N bond formation to provide benzocarbazoledione 5
(Scheme 6). Similarly, on treatment of compound 4a with
Pd(OAc)29c in AcOH the same compound 5 was obtained. Earlier
benzocarbazoledione was reported via [3+2] cycloaddition of
arynes with 2-Aminonapthowuinone.9d Benzocarbazoledione
derivatives shows antibiotic and antitumour9a activities.
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Scheme 6. Synthesis of benzocarbazoledione from N as well C-
aryl naphthoquinones
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In conclusion we have developed a novel transition
metal mediated method for selective C vs N arylation of 2-
amino-1,4-naphthoquinone using arylboronic acids. In the
presence of Mn(OAc)3.2H2O, C-arylation took place at C-3
position of 2-aminonaphthoquinone (1a) whereas in the presence
of NiCl2.6H2O, N-mono arylation took place exclusively. In case
of Cu(OAc)2.H2O, N-mono arylation as well as N,N- diarylation
occurred. In general, moderate to good yield of product was
obtained. This study is an example of how transition metal
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catalysts could be used for fine tuning reactivity of
a
multifunctional substrate. Furthermore, the synthetic utility of the
compounds obtained from the present study was demonstrated by
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19. Satoshi, U.; Mingjuan, S.; Buchwald, S. L. J. Am. Chem. Soc.
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Acknowledgments
P.A. thanks UGC, New Delhi, for the award of RFSMS
fellowship. We thank DST-FIST for the use of their instrument
facility at the School of Chemistry, Bharathidasan University.
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Supplementary Material
Supplementary material that may be helpful in the review
process should be prepared and provided as a separate electronic
file. That file can then be transformed into PDF format and
submitted along with the manuscript and graphic files to the
appropriate editorial office.
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