【作者】 张锦辉；

【导师】 江焕峰；

【作者基本信息】 华南理工大学 ， 化学， 2024， 硕士

【摘要】 烯烃作为一种石油工业的大宗产品,被广泛应用于合成砌块的构建和化工产品的生产过程。在烯烃的官能团化领域,将钯催化烯烃的环化反应用于构建氮/氧杂环骨架一直是研究的热点课题。近年来,随着绿色化学的不断发展以及人们对反应选择性和经济性的持续关注,如何高效简洁地构建各种具有独特理化性质和重要应用价值的杂环化合物对科研工作者提出了更高的要求。基于此,本论文以具有多个活性位点的3-丁烯酸和廉价易得的芳胺作为底物,分别发展了由C-H键活化和亲核钯化启动的钯催化非活化烯烃的环化反应,在简单高效的反应条件下,构建了包含γ-丁内酯在内的含氮杂化骨架。具体研究内容如下:(1)本文在第二章中研究了钯催化3-丁酸与芳胺的氧化环化反应。该催化体系通过N-α-C(sp~3)-H键和苯环C(sp~2)-H键活化,高效地合成了一系列γ-丁内酯环合的1,2,3,4-四氢喹啉衍生物。该反应条件温和,具有优异的非对映选择性,且底物适用性广,官能团容忍度高,能很好地兼容某些高度敏感的基团。值得注意的是,该策略能够在一锅法中完成三根化学键的形成和一个二元并环骨架的构建,显示出较高的原子经济性和步骤经济性。KIE实验表明,C-H键的断裂可能不涉及反应的决速步。(2)本文在第三章中研究了钯催化3-丁烯酸与2-乙炔基苯胺的1,1-胺氧化/环化反应。该反应操作简便,无需预先安装外源导向基,对带不同类型官能团的底物都表现出良好的兼容性,以高原子经济性和高步骤经济性的方式构建各种具有潜在应用价值的5-(1H-吲哚-1-基)-二氢呋喃-2-(3H)-酮类化合物,实现了钯催化未活化烯烃的1,1-双杂化反应。该反应由分子间胺钯化启动,涉及β-H消除、氧化、互变异构、氧钯化、分子内胺钯化等串联步骤。值得注意的是,2,9-二甲基-1,10-菲罗啉配体的加入是实现分子间胺钯化的关键,能有效地抑制吲哚副产物的产生。更多还原

【Abstract】 Alkenes,a bulk product of the petroleum industry,which are widely used in the construction of synthetic blocks and the production of chemical products.In the field of functionalization of alkenes,the palladium-catalyzed annulation reactions of alkenes for the construction of N/O heterocyclic skeletons have been a hot topic of research.In recent years,with our increasing concern for green chemistry and the selectivity and economics of reactions,how to construct various heterocyclic compounds with unique physicochemical properties has put forward higher requirements for researchers.In this thesis,a set of palladium-catalyzed unactivated alkene annulation reactions initiated by C-H bond activation or nucleopalladation have been developed.These reactions employ readily available 3-butenoic acid and aromatic amines as the substrates,enabling the building of nitrogenous heterocyclic skeletons withγ-lactones under mild reaction conditions.The specific research works are as follows:In chapter two,a palladium-catalyzed oxidative cyclization reaction of 3-butenoic acid with aromatic amines via the activation of N-α-C(sp~3)-H and C(sp~2)-H bonds was developed for the efficient synthesis ofγ-lactone fused tetrahydroquinolines.The remarkable characteristics of this reaction include excellent diastereoselectivities,broad substrate scope and good tolerance for some highly sensitive groups.In addition,three chemical bonds are formed and a fused bicycle is efficiently constructed in one step,showing a high step economy.Notably,the KIE experiment suggested that C-H bond abscission is not the turnover-limiting step.In chapter three,a palladium-catalyzed intermolecular 1,1-aminoxylation/cyclization of 3-butenoic acid and 2-ethylanilines providing 5-(1H-indol-1-yl)-dihydrofuran-2-(3H)-ones without preinstalling exogenous directing groups.The reaction tolerates a wide range of functional groups,which may be initiated by intermolecular aminopalladation and involves aβ-H elimination/tautomerization/oxidation/oxopalladation/intramolecular aminopalladation cascade pathway.An external ligand,2,9-dimethyl-1,10-phenanthroline,has been used to succeed in this protocol to inhibit the production of indole byproducts.更多还原