Study On Copper-promoted Cyclization Of ??amino Nitrile-Tethered 1,7-Enynes

Rapid and e readily available starting materials represent an appealing efficient construction of structural complexity fromand significant challenge in organic synthesis.The transition metal-catalyzed cyclization of enynes offers an attractive pathwayfortheconversionofrelativelysimpleacyclicsubstratestoa varietyof valuable cyclic compounds which have been difficult to prepareby conventional methods.1 Recently,the versatile cyclizationchemistry of enynes has made possible the construction ofvaluable functional bicyclo[4,1,0]alkene frameworks by means oftransition-metalcatalysts.Typically,thepresenceofelectronrich C-C double bond component is to be pivotal to theaccomplishment of this electrophilic activation-involved transformation in which the N,O,or C atom bridged the C-C triplebond and double bond units,while the cyclization ofenynes incorporating an electronically deficient C-C doublebond proved to be challenging and has been never reported.Among the extraordinary variety of metal-catalyzed reactions,enyne rearrangements aregrowing in importance asdepending on the functional groups and the experimentalconditions-several transformations are possible which lead to cyclic derivatives.Suchmetal-catalyzed processes are inherently atom economical and result in a significant increase instructural complexity.In general,they are operationally simple,safe,and convenient to performeven on a large scale.This review will attempt to emphasize historical and major contributions tothe field and will focus on the applications in total synthesis of natural or biologically activeproducts.We designed and developed a kind of nitrogen-tethered 1,7-enynes bearing an election-withdrawing group on olefins,under the catalysis of transition metal cyclization rearrangement to synthesis of 3-azabicyclo[4,1,0] heptyl diene with cyclopropane the structure unit.The content of this research paper mainly includes the 3 parts:(1)Azepine has significant pharmacological and biological activity,and scientists have developed a number of methods for the preparation of heterocyclic rings containing acridine heterocycles.In this paper,a novel method was developed to synthesize 4,5-dihydro-3H-aza-membered ring acridine by copper catalyzed cyclization of 1,7-enyne containing ?-amino nitrile compounds.(2)Synthesis of azabicyclo [4,1,0] heptadiene by coupling-cyclization reaction,coupling with iodobenzene and its substituted compounds with 1,7-enyne terminal alkynes,And further cyclization reaction occurs.This method realizes the cyclization of the inner alkyne under copper catalyzed conditions to obtain azabicyclo [4,1,0] heptadiene with two benzene ring structures.(3)In this paper,nitrogen-substituted azabicyclo [4,1,0] heptadiene was synthesized by one-pot coupling / cyclization reaction.The method is simple and rapid,and it saves the steps of post-treatment.It is a green synthetic method with atomic economy,but it is regrettable that this method is not suitable for asymmetric amine.