Communication
ChemComm
immediately oxidized to form the allenol radical intermediate
9 (a) L.-W. Ye, X.-Q. Zhu, R. L. Sahani, Y. Xu, P.-C. Qian and R.-S. Liu,
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(II).
Next, the azide group was attacked directly by the oxygen
radical to afford intermediate (III), which was then captured by
a hydrogen radical to give intermediate (VI). Finally, the inter-
mediate (VI) goes through an aromatization process to afford
product 2a. The initial designed process, that the azide group
was attacked by a carbon radical to give intermediate V, was
2
020, 59, 10396; (d) H.-M. Jin, L. Huang, J. Xie, R. Matthias, R. Frank
and A. S. K. Hashmi, Angew. Chem., Int. Ed., 2015, 55, 794;
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(
(
Chem. Sci., 2019, 10, 1201.
0
unrealized. Thus, product 2a was not observed. The whole
1
0 (a) J. Li, E. Tan, N. Keller, Y.-H. Chen, M. Z. Peter, C. J. Andreas,
B. Thomas and K. Paul, J. Am. Chem. Soc., 2019, 141, 98; (b) S.-J. Yu,
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reaction process showed excellent chemoselectivities.
In conclusion, a new strategy has been developed for the
synthesis of anthranils under metal free conditions. Excellent
chemoselectivity was seen in the product, as the azide group
was attacked exclusively by oxygen radicals. The synthesized
anthranils are important N-heterocycles, which can be
employed as masked N-nucleophiles in various transforma-
tions. For example, the weak N–O bonds could be cleaved in
the presence of Cu(I)-salts or Pd/C and go through aminations
with 2-oxo-2-phenylacetic acid and iodobenzene.
Financial support from the National Natural Science Foun-
dation (21702065, 21772046 and 2193103) and the Promotion
Program for Young and Middle-aged Teachesr in Science and
Technology Research of Huaqiao University is gratefully
acknowledged.
2
0, 4010.
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2040 | Chem. Commun., 2021, 57, 2037ꢀ2040
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