A Survey About The Cyclization Reactions Involved In Two Kind Of Metal Carbene Precursors And D-A Cyclopropanes

This thesis focused on the survey about the cyclization reactions involved in two kind of metal carbene precursors and D-A cyclopropanes,mainly includes the following five parts.Chapter 1:We firstly make a brief introduction about the history of metal carbene and its research progress.Then the recent advances about the structural features and reaction activity of several commonly used metal carbene precursors were described.The active metal carbene are important synthetic intermediate which could participate in various types of useful transformations,such as cyclopropanations,X-H insertions,dipolar cycloadditions,migratory insertions and cross coupling reactions.Chapter 2:High order cycloaddition reaction is an efficient stragtety for the construction of middle sized ring system.In this chapter,N-sulfonylated1,2,3-triazoles are used as the precursor for rhodium?II?azavinyl carbene,which can act as an aza-[3C]synthon in the[8+3]high order cycloaddition with8-azaheptfulvenes to yield the cyclohepta[b]pyrazine derivatives.Moreover,the cyclohepta[b]pyrrolone derivatives are generated by the reaction between?-carbonyl diazo compounds and 8-azaheptfulvenes via a[8+2]process.Chapter 3:The N-O containing heterocycles are important structural motifs which spreaded in a variety of natural products.Dipolar cycloadditions of nitrile oxides are the most direct method for the synthesis of this kind of heterocycles.In this chapter,the N-sulfonylated 1,2,3-triazoles and 3?diazoindolin-2-imines are utilized for the generation of metal carbene intermediates which could react with nitrile oxides to yield various N-O containing five-membered heterocycles.An oxidation reaction of metal carbene with oxygen is involved in the reaction system.Chapter 4:Cyclopropane-fused indolines are not only important structural motifs,but also useful synthons for the synthesis of indoline alkaloids.The conjugated ene-yne-ketones are used as carbene precursors for the cyclopropanation of directing group substituted indoles catalyzed by low-cost ZnI₂.And a series of highly functionalized cyclopropane-fused indolines are generated with excellent yield and diastereoselectivity.Chapter 5:The D-A cyclopropanes are used as versatile[3C]-synthons in plentiful attractive transformations.In this chapter,Sc?OTf?₃ is used as the catalyst to promote the tandem Friedel-Crafts alkylation/Michael addition reaction of cyclopropane 1,1-diesters and indole derivatives.A varity of multi-substituted tetrahydrocarbazoles are obtained with high yield,and they are bioactive motifs ubiquitous in natural products.