Enhancing C–N bond formation in amine carbonylation through dual hydrogen bonding catalysis under mild reaction conditionsOA
The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton transfer mechanism remains elusive.Herein,we reported a metal-free,room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)as a dual hydrogen bond catalyst to synergistically activate propylamine(PA)and dimethyl carbonate(DMC).This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions.This is enabled by dual hydrogen bonding of TBD with PA and DMC,which facilitates rapid proton transfer and stabilizes tetrahedral intermediates.Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs.Furthermore,it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate.This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.
Xiang Hui;Jianhui Shi;Jiajun Zhang;Yan Cao;Huiquan Li;Peng He;Liguo Wang
CAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,ChinaCAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,ChinaCAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,ChinaCAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,ChinaCAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,China School of Chemical Engineering,University of Chinese Academy of Sciences,Beijing,100049,ChinaCAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,ChinaCAS Key Laboratory of Green Process and Engineering,National Engineering Research Center of Green Recycling for Strategic Metal Resources,Institute of Process Engineering,Chinese Academy of Sciences,Beijing,100190,China School of Chemical Engineering,University of Chinese Academy of Sciences,Beijing,100049,China
化学化工
Dual hydrogen bondsCarbonylation reaction-C-N-bondProton transferMild conditions
《Green Energy & Environment》 2026 (1)
P.236-247,12
financially supported by the National Key R&D Program of China(2023YFC3905400)the Clean Combustion and Low-carbon Utilization of Coal,Strategic Priority Research Program of the Chinese Academy of Sciences,Grant No.XDA 29000000.
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