布朗斯特酸催化的1 6烯炔环异构反应研究-catalytic isomerization of 1,6 - enylene ring catalyzed by bronsted.docxVIP

兰州大学硕士学位论文陈锦ABSTRACTThechemicalbehaviorof1,6-enynesubstrmeviatransitionmetalcatalysthasbeenextensivelystudied．The1,6·enynecycloisomerizationgetsthefollowingcharacteristics：startingfromtheopenchainsubstratecallbeefficientlysynthesizedcycliccompounds；withatomeconomy；caneasilyobtainthe1,3-and1,4dieneproduct．Thesefeaturesattractedtheinterestofchemists．Afternearlytwodecades，thistypeofreactionhasbeengreatdevelopment．Uptonow,scientistshasdevelopedavarietyoftransitionmetalcatalystsystem．Andthedifferenceoftheregionalselectivity，stereoselectivityleadtodifferent}eactionresults．Thekeyofthispaperisthatdifferentfromthetraditionaltransitionmetalcatalysis，researchingonBronstedacidcatalyzed1,6-enynecycloisomerizationbyhighefficiencyandconvenientreaction．ThedivinylproductWasfoundforthefirsttime．2．0mmolof1，6一enynewith0．1mol％ofcatalystinDCMf2．0mE)at0℃．Intheinvolvementofwatermolecules，the1．6一enynewascycloisomerizedtogiveseriesofdivinylproducts．andtheyieldwasin56％．84％．respectively．ThestructuresofproductswerefurtherconfirmedbyfiomIR,1HNM＆1jCNMRspectrasandelementalanalysis．Inaddition,onthebasisoftheelectronsandstructuresofproducts，weestablishedthemechanismofthisreactioninanexperimentalmanner：hydrogenprotonsthroughtheprovisionofBronstedacidactivationofacetylenebase，inducedalkenylasnucleophilicattack,andcompletetheril唱ofring—dienederivativesgeneratedtogether．Keywords：1，6．enyneBronstedacidefficientdienecycloisomerization6兰州大学硕十学位论文陈锦缩略词简表AcAcetyl／7,酰基AIBNAzodiisobutyronitrile／偶氮二异丁腈ArAryl／3基BnBenzyl／苄基BuButyl／丁基BzBenzoyl／苯甲酰基DCCDicyclohexylcarbodiimide／--环己基碳二亚胺de．Diastereomericexcess／：llz对映异构体过量DIADDiisopropylazodicarboxylate／偶氮二甲酸二异丙酯DIBAmDiisobutylaluminumhydride／二异丁基氢化铝DMAP4-N,N-Dimethylaminopyridine／4-Ⅳ，Ⅳ-二甲氨基吡啶DMPDess-Martinperiodinane／l，1，l-三乙氧酰基-1，1．二羟基一l，2一苯碘酰一3(1月)．酮DMSDimethylsulfide／二甲硫醚DⅣⅢN,N-Dimethy’lformamide／Ⅳ，Ⅳ-二甲基甲酰胺DMSODimethyIsulfoxide／二甲基亚砜Dppe(diphenylphosphino)ethane／1,2--(-苯膦基)乙烷e．e．EnantiomericeXCeSS／对映异构体过量eq．Equivalent／当量EtEthyl／7,基Hrshour／4,时HMDS1，1，l，3，3，3-Hexamet