Amination Of Propargyl Alcohol And N-fluoroarylsulfonimides(NFSI):Synthesis Of Allenamide Derivatives

Allenamide compounds are important class of organic synthesis intermediates.These compounds can be used to synthesize natural products with biological or drug activity.Allenamide compounds are also important structural fragment of drug-active molecules.At present,many methods have been developed for the synthesis of allenamide compounds,such as base-induced isomerizations of propargyl amide,sigmatropic rearrangements,eliminations,amino-cyclizations and Trost-Hsung N-allenylations.Although these methods can be used to synthesize allenamide compounds,they still have some shortcomings,including not readily available substrates,harsh reaction conditions,limited scope of substrates or requirement of precious metals.Therefore,it is desirable to develop a new method for the synthesis of allenamides starting from easily available materials under mild reaction conditions with simple operation.In this thesis,the amination reaction of propargyl alcohol with N-fluoroarylsulfonimides(NFSI)was carried out,and a series of allenamide compounds were synthesized.The thesis is divided into two parts: One was the amination reaction of propargyl alcohol with NFSI.Using readily available propargyl alcohol as starting material,NFSI as amination reagent,under mild conditions,allenamides were efficiently synthesized.The other one was the study on reaction mechanism.Through controlled experiments and literature research,we proposed that NFSI is used as Lewis acid in the amination reaction to activate propargyl alcohol for the formation of propargyl carbocation,which then resonated to an allene carbocation.Finally,the nucleophilic amination reaction occurred,leading to allenamides.In this thesis,the amination of propargyl alcohol and NFSI was efficiently realized,providing a series of allenamides.The reaction has the advantages of a wide rang of substrates,simple operation and insensitivity to air and water.The novel amination reaction provides a new method for the synthesis of allenamide compounds.