Study On The [3+2] Cycloaddition/double Ring Opening/chlorination Tandem Reaction Initiated By Furanmethyl Carbanion

Furan compounds have attracted much attention from chemists,as a cheap and easily available renewable biomass.Rearrangement of furan-based compounds has become an important strategy in synthetic chemistry.The development of reaction methods based on furan is of great significance for improving the wide application of furan in organic chemistry,pharmaceutical chemistry,material chemistry and other fields.Chlorine-containing molecules have gained considerable attention owing to their widespread applications in organic synthesis as versatile building blocks and intermediates.A large number of natural products contain chlorine and lany ot them show significant bioactivity.Additionally,more than 70%of all pharmaceutical products possess chlorine or are produced using chlorine.The general chlorination reaction is start from an active functional group,such as a hydroxyl group,a carboxyl group,a diazo group or an unsaturated bond(alkenyl/alkyne).The importance of the development of synthetic methods for C(sp3)-Cl bonds construction has been continually pursued using atom-econoly and step-econoly principles.Based on the previous work,we have developed a new cascade formal[3+2]cycloaddition/double ring-opening/chlorination methodology.Furylcyclobutanol and azide compounds was selected as substrates,and TiCl4 as a carbocation initiator.A series of trisubstituted complex triazoles with a 3-chloropropyl unit and an(E)-enone moiety were synthesized by this method.During the reaction,TiCl4 was not only as a carbocation initiator for the reaction but also as a source of chlorine element for the chlorination.This highly efficient transformation involves the formation/cleavage of several C-N,C-Cl,C-C,and C-O bonds in a single operation.And the related data of 1H NMR,13C NMR,high resolution mass spectrum,and melting point of the synthesized compound were collected.The method has good atomic economy and step economics.The full text is divided into three parts.The first chapter:the application of the rearrangement reaction of furan compounds in organic synthesis and the research background of triazole compounds.The second chapter:Based on the previous work of our group,we explored the furfuuyl cation induced cascade formal[3+2]cycloaddition/double-ring-opening/ch-lorination reaction.And 20(E)-3-chloropropylketene triazoles compounds were synthesized.The research status of chlorination reaction is also introduced.The third chapter:the part of experiment and spectroscopic date of product.