The Hydroamidation And Hydrophosphorylation Of Ynamides

The functionalization of alkynes is one of the significant strategies for C-C and C-heteroatom bond formation in modern organic chemistry.Ynamides,bearing an additional electron-withdrawing group on the nitrogen atom,display many advantages such as thermal stability,synthetic accessibility,and easyhandling over their ynamine congeners due to the optimalbalance between stability and reactivity.Recently,the functionalization of ynamides has received much attention in organic synthesis as the development of many synthesis methods of ynamide.Our group has a great interest in ynamide chemistry and reported?-addition of ynamides with carboxylic acids.Herein,we have developed an excellent regio-and stereoselectivities,hydroamidation hydro–phosphorylation and hydrophosphination of ynamides through a trans-?-addition reaction with transition-metal free.This paper mainly includes the following two parts of research content:?1?An excellent regio-and stereoselectivities hydroamidation of ynamides with primary amines to furnish?Z?-?-endiamide in the presence of Cs₂CO₃ under room temperature is developed.This strategy provides a novel method for the synthesis of1,2-diamide.?2?An excellent regio-and stereoselectivities hydrophosphorylation and hydrophosphination of ynamides with P-H compounds such as diphenylphosphine,diphenylphosphine oxide and dialkyl phosphateto furnish?Z?-?-phosphor-enamide in the presence of Cs₂CO₃ under room temperature is developed.This strategy providesnot only a novel method for the C?sp²?-P formation but also the 1,2-N,P compounds that could be used as potential ligand precursors.