Communication
ChemComm
Notes and references
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´
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With the deprotonation of 1a by DPG, the in situ generated
homopropargyl amine anion coordinated to the DPG–Ag(I) to
form the intermediate B. Then the reaction with CO2 gave the
carbamate intermediate C, which could be stabilized by DPG
via possible H-bonding interactions. The simultaneous inter-
action of the carbamate and alkyne moiety with the DPG–Ag(I)
complex facilitated the subsequent nucleophilic addition,
affording the desired 2-oxazinone 2a effectively. Notably, during
the reaction, CO2 could be reversibly trapped by DPG, thus
enhancing the effective concentration of the reaction system,
and finally enabled the reaction to proceed effectively.
In summary, we have found that the simple and easily
available DPG, bearing three N–H bonds, could trap and release
CO2 under ambient conditions via the formation of crystalline
H-bonded bicarbonate dimers. Based on this discovery, the
unprecedented highly efficient carboxylative cyclization of
homopropargyl amine with CO2 under ambient temperature
and pressure was realized. The combination of DPG with
AgSbF6 enabled the facile synthesis of both chiral and achiral
2-oxazinones in good to excellent yields with CO2 as the C1
synthon. A mechanism study revealed that the multifunction-
ality of DPG is critical. Apart from enhancing the effective
concentration of CO2 in solution via trapping and releasing
CO2 under ambient conditions, it could also serve as a neutral
monodentate ligand to coordinate with AgSbF6 in a head-to-
head fashion, as demonstrated by X-ray diffraction data, thus
improving the efficiency of the reaction. The development of
other novel CO2 participating chemical transformations for the
synthesis of value-added chiral chemicals is now in progress in
our laboratory.
´
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14 In our previously reported carboxylative cyclization of N-aryl pro-
pargylanilines with CO2, DPG also showed unique activity compared
to other bases, such as DBU, TMG and TPG. The representative
results are shown below, for details see ref. 6b
We gratefully acknowledge the 973 Program (2015CB856600),
NSFC (21871090, 21573073) and Fundamental Research Funds
for the Central Universities for financial support.
Conflicts of interest
There are no conflicts to declare.
15 G. Fang and X. Bi, Chem. Soc. Rev., 2015, 44, 8124–8173.
14306 | Chem. Commun., 2019, 55, 14303--14306
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