三氟甲基重氮甲烷在有机合成中的应用  

The application of trifluoromethyl diazomethane in synthesis

作　　者：魏威 霍孟田 宁永泉 WEI Wei;HUO Meng-tian;NING Yong-quan(Department of Chemical and Environmental Engineering,Changchun University of Science and Technology,Changchun 130022,China;Faculty of Chemistry,Northeast Normal University,Changchun 130024,China)

机构地区：[1]长春理工大学化学与环境工程学院,吉林长春130022 [2]东北师范大学化学学院,吉林长春130024

出　　处：《分子科学学报》2022年第2期109-136,共28页Journal of Molecular Science

基　　金：博新计划资助项目(BX20200079)。

摘　　要：三氟甲基重氮甲烷是一种活泼的重氮试剂,与重氮甲烷、重氮乙酸乙酯一样可以发生卡宾反应、偶极环加成反应等多种反应;相比于其他重氮试剂这种化合物的独到之处在于能有效、原子经济地向分子内引入三氟甲基.本文从三氟甲基重氮甲烷的制备方法和反应性能两方面进行论述,着重综述了近十余年以来三氟甲基重氮甲烷的卡宾反应、偶极环加成反应等多种反应在有机合成中的应用,从而展示具有广泛用途的三氟甲基化合物的优良合成方法.Trifluoromethyl diazomethane is a kind of active diazo reagent,which can produce carbene reaction,dipole cycloaddition reaction and other reactions like diazomethane and ethyl diazoacetate.This compound,however,is unique in that it can introduce trifluoromethyl into the molecule more efficiently and economically than any other diazo reagent.Trifluoromethyl(CF_(3))is the basic structural unit of various organofluorine compounds.The strong electronegativity,excellent stability and lipophilicity of this group can often lead to unexpected optimization of the properties and even physiological activities of organic molecules.Therefore,the synthesis of trifluoromethyl-containing compounds using cheap and readily available raw materials and reagents is an important and hot research topic.Trifluoromethyldiazomethane(CF_(3)CHN_(2)),as a functionalized diazoalkane,has high efficiency and atom economy by using this compound to introduce trifluoromethyl into organic molecules.Therefore,it has attracted extensive attention of organic synthesis workers in recent years.As an important trifluoromethyl building block,trifluoromethyldiazomethane can have many types of reactions.In the past ten years,there have been reported[3+2]cycloaddition reactions with dipoles as 1,3-dipoles,nucleophilic reactions with aldehydes,ketones,imines,etc.as carbon nucleophiles type reaction,based on carbene(metallic carbene popular in recent years)insertion and[2+1]cycloaddition reaction.This review describes the development of trifluoromethyl diazomethane chemistry over the years and summarizes its reactivity.In general,there are the following categories:(1)[3+2]dipolar cycloaddition reactions;(2)[3+3]cycloaddition reaction;(3)ionic reaction as nitrogen electrophile;(4)ionic reaction as carbon nucleophile;(5)reaction based on carbene mechanism,etc.Although the research on trifluoromethyl diazomethane has made great progress,it still faces the dilemma that the substrate scope needs to be improved,the cost needs to be reduced,and a large number of reac

关 键 词：三氟甲基 重氮化合物 卡宾反应 偶极环加成 催化方法 

分 类 号：O623[理学—有机化学]