Construction Of Novel Bis(ethoxycarbonyl)glycoluril Macrocycles Based Mannich Reaction

Macrocycles possessing novel skeletons with new function have attracted much attention in diverse areas such as drug development,material sciences and supramolecular chemistry.Among diverse strategys for synthetic macrocycle efforts,Mannich reaction has contributed a lot as its widely common substrates and mild reaction condition.'Active-hydrogen' s component condensed with amines and formaldehyde via Mannich reaction to synthesis various macrocycles with novel skeletons has long been reported.In this dissertation,we have investigated a new class of macrocycles possessing bis(ethoxycarbonyl)glycoluril backbond mainly based Mannich reaction assembling with other alkyne reaction,and the main content is as follows:In chapter 1,firstly we summed up the application of Mannich reaction in synthetic diverse novel macrocycles,classified based on important component which provided active-hydrogen.As we discovered macrocycles containing glycoluril skeleton or propargylamines backbond are not commonly reported,so we combined Li's work synthesis of molecules clip by Mannich reaction from bis(ethoxycarbonyl)glycoluril and our previous work prepared macrocycles from diyne via Mannich reaction.Finally we designed to construct novel macrocycles including bis(ethoxycarbonyl)glycoluril based bis-Mannich reaction.In chapter 2,as the importance of propargylamines,we continue our preliminary work of macrocycles possessing propargylamine skeleton.An detailed research of molecules clip diyne la and macrocycles including propargylamines was undergoed.First glycoluril,propargylamine and formaldehyde yields diyne 1a via Mannich reaction,and then la,formaldehyde with diversity di-secondary amines yields macrocycles 2a-2f.All the compounds of macrocycles are characterized by 1H NMR,13C NMR,IR and HRMS.In additional,la and 2a were further confirmed by X-ray single crystal diffraction.Macrocycles 2a had cavity and was potential receptor to recognition micromolecule.In chapter 3,diversity-oriented synthesis(DOS)strategy was used synthesis macrocycles including bis(ethoxycarbonyl)glycoluril when la was used as common substrate.Assembling Mannich reaction with alkyne homocoupling reaction we yields macrocycle 3a which contained glycoluril and diacetylenic groups and was confirmed by X-ray single crystal diffraction.Assembling Mannich reaction with click chemistry we yields a novel macrocycle 3b containing glycoluril and triazole.