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Finally, according to the above conclusion, we propose the
possible mechanism (Scheme S2): The oxidation addition of
iodobenzene and Pd (0) produces palladium intermediate I. PPh3
or LN9 can catalyze the reaction alone, so the palladium ligand
can be any either of them. The reaction mechanism of only
adding pivalic acid should be special, requiring further study in
the future. Subsequently, the migration and insertion reaction of
E. Farmer and J.-Q. Yu, Angew. Chem. IDnOt.I:E1d0..1,023091/D70, C56C,063784794D-
6877; (d) P.-X. Shen, X.-C. Wang, P. Wang, R.-Y. Zhu and J.-Q.
Yu, J. Am. Chem. Soc., 2015, 137, 11574-11577; (e) H. Shi, A.
N. Herron, Y. Shao, Q. Shao and J.-Q. Yu, Nature, 2018, 558,
581-585; (f) H. Shi, P. Wang, S. Suzuki, M. E. Farmer and J.-Q.
Yu, J. Am. Chem. Soc., 2016, 138, 14876-14879; (g) P. Wang,
M. E. Farmer and J.-Q. Yu, Angew. Chem. Int. Ed., 2017, 56,
5125-5129; (h) P. Wang, G.-C. Li, P. Jain, M. E. Farmer, J. He,
P.-X. Shen and J.-Q. Yu, J. Am. Chem. Soc., 2016, 138, 14092-
14099.
intermediate
I
with norbornene and the ortho-C(sp2)-H
activation occurs to form ANP intermediate II. This process is a
kind of CMD process promoted by cesium carbonate. The
coordination between iodine and cesium may occur, so the cation
of carbonate has an important influence on the reaction.18 Next,
ANP intermediate II and electrophilic amination reagent 2
undergo an oxidation addition or concerted addition process to
generate the ortho-C-H amination intermediate IV, and then the
β-carbon elimination process occurs to produce intermediate V.
According to our previous work, intermediate V and Cesium
valerate undergo a carboxylic acid exchange process to generate
intermediate VI.19 Finally, intermediate VII is formed by
migration and insertion with alkyne 3, and the intermediate VII
then undergoes two different processes to produce target product
4.
In summary, this report described the first DMAP and
PivOH-promoted ortho-C-H amination and ipso-allenization
reaction of iodobenzenes realized by Pd/norbornene cooperative
catalysis. Non-terminal alkynes were used as the allenization
reagents, and allenization was completed through the concerted
metalation deprotonation (CMD) and β-hydrogen elimination
process. Through control experiments and DFT calculations, we
discussed the mechanism of the three ligands in the reaction
5
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Financial support was received from the National Natural
Science Foundation of China ((NSF 21472073,21772075 and
21532001). Computations reported in this paper were performed
on the computer clusters at the Centre for Scientific Modeling
and Computation, CUHK.
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Conflicts of interest
There are no conflicts to declare.
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