低价钛介入下脂肪族酰胺和脂肪族醛/酮的还原偶联反应研究
Project Number21462025
苏策
Abstract利用酰胺氮原子上取代基的电性效应,调节酰胺羰基的还原电位以及与低价钛试剂的配位作用,只要其第二还原电位小于脂肪族醛/酮的还原电位,酰胺羰基即可快速、不可逆地从低价钛试剂接受两个电子生成双负离子中间体,促使反应按照双负离子机理进行,实现反应的选择性控制;酰胺双负离子对醛/酮亲核加成形成钛频哪醇盐中间体,低价钛试剂的模板效应促使其氧原子在同一活性钛粒子表面配位,利于随后的脱氧消除。本项目通过原位还原与偶联组分配位的钛试剂,形成瞬间的低价钛物种促进脂肪族酰胺和脂肪族醛/酮的还原偶联,系统考察各种反应条件对该分子间McMurry偶联的影响、反应的底物普适性和官能团耐受性,设计各种对比实验,结合电化学实验和谱学方法,验证可能的反应机理,建立酰胺与醛/酮间交叉还原偶联的方法学;通过脂肪族酰胺和醛酮的分子内偶联,建立环烯胺的合成方法,并尝试用于【m.n.0】-双环-1-氮杂烷烃生物碱骨架的构建。【英文摘要】Amidewouldreceivetwoelectronsfromlowvalenttitaniumquicklyandirreversiblytoformanamidedianionpriortoanyelectrontransfertoanaliphaticaldehyde/ketonecarbonyl,solongassecondreductionpotentialofamideisadjustedtolessnegativethanaaldehyde/ketonecarbonylbymeansofelectroniceffectofthesubstituentsattachedtoamidenitrogen,consequently,leadingtoadianioncouplingmechanismandthisprocesswouldpermittheselectivitycontrolling.Thenucleophilicadditionofamidedianiontoaldehyde/ketonecarbonylresultedintitaniumpinacolate,withitstwooxygensbothcoordinatingtoasameactivetitaniumparticlesurface,thistemplateeffectwouldensurethesubsequentdeoxygenativeelimination.Followingthislineofreasoning,theprojectisaimingatthedevelopmentofMcMurrycouplingbetweenvariousaliphaticamidesandaliphaticaldehydes/ketoneseffectedwithanactivetitaniumspecieswhichispreparedfrominstantreductionofTiCln(n=3,4)coordinatingtobothcouplingpartners.Onthebasisofextensiveinvestigationsofvariousreactionconditions,substrategenerality,functlonal-groupcompatibility,andcontrastexperimentswithdesignedsubstratesbearingappropriatestructuralprobes,meanwhile,withthehelpofelectronchemicalinvestigationsandspectroscopicmethods,apossiblemechanismforsuchintermolecularamide-aldehyde/ketonecouplingprocesseswouldbeproposed,thus,thecorrespondingsyntheticmethodologyhavebeendeveloped.Extendingthiscrosscouplingreactiontointramolecularcontexts,theapproachestocyclicenaminesshouldbeestablished,inturn,m.n.0-bicyclo-1-azaalkane(izidine)structuralmotifembeddedwithinnumerousknownalkaloidscanalsobeconstructed.
Subtype地区科学基金项目
Project Source国家自然科学基金
2015-01
End Date2016-12
MOST Discipline Catalogue05 - 化学科学 ; 0501 - 合成化学
Host Institution兰州理工大学
Project Funding250000.0
CountryCN
Language中文
Document Type项目
Identifierhttp://ir.lut.edu.cn/handle/2XXMBERH/64744
Collection石油化工学院
Recommended Citation
GB/T 7714
苏策.低价钛介入下脂肪族酰胺和脂肪族醛/酮的还原偶联反应研究.2015.
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