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led to the products in moderate to good yields (3ab-3ag).
Intriguingly, unsymmetric 1-phenyl-3,3-diethoxy-1-propyne was
applied as a coupling partner, and it proceeded smoothly to afford
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4
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[
7
3
ah (CCDC: 2050115) in 84% yield with high regioselectivity
Section 2.5 in Supporting information). However, when 1-phenyl-
-pentyne was applied, a mixture of regioisomers 3ai and 3ai' was
produced.
To understand the chemo-selectivity of this reaction, we
[8] T.K. Hyster, T. Rovis, J. Am. Chem. Soc. 132 (2010) 10565–10569.
(
1
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1
[
[
performed a series of density functional theory (DFT) calculations
using 1,2-diphenylacetylene (2a) and amide 1d as the substrates
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[
57–61]. The calculations demonstrated that the reaction pro-
[
[
[
[
ceeded through a C–H activation, alkyne insertion, and metal-
lallylcarbenoid annulation (Scheme 4, for computational details,
see Section 2.6.2 in Supporting information) [62]. The chemo-
selectivity was determined in the C ÀÀ H activation step via
transition states TS-N-Ag-1 (17.6 kcal/mol) and TS-O-Ag-1
[
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4
(
22.2 kcal/mol). Therefore, the N-directed pathway was favored
[
over O-directed pathway by 4.6 kcal/mol, in agreement with that
only N-cyclization product 3da is observed in the presence of
(
[
E
Cp Rh catalyst. In the N-directed pathway, the C ÀÀ H activation step
(
(
(
via TS-N-Ag-1) is 1.7 kcal/mol higher than the alkyne insertion
via TS-N-Ag-2) indicating an ambiguous kinetic isotope effect. The
[
5
kinetic isotope experiments were conducted with 1d and 1d-d
under standard reaction conditions (parallel experiment:
= 1.50 and intermolecular: k /k = 1.55), which were consis-
tent with DFT calculations.
In summary, we have successfully developed a selective N-
annulation of benzamides with internal alkynes under mild
5
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k
H/
k
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[
reaction conditions with an electron-deficient catalyst
9
E
[
Cp RhCl
2
]
2
. The electronic effect of ligand played a vital role in
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Declaration of competing interest
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(
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
[
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Acknowledgments
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We gratefully acknowledge the National Natural Science
Foundation of China (Nos. 21671097 and 21573106) and the
Fundamental Research Funds for the Central Universities for
financial support.
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