| 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 Number | 21462025 |
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 Date | 2016-12 |
| MOST Discipline Catalogue | 05 - 化学科学 ; 0501 - 合成化学 |
| Host Institution | 兰州理工大学 |
| Project Funding | 250000.0 |
| Country | CN |
| Language | 中文 |
| Document Type | 项目 |
| Identifier | https://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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