【作者】 杨芳；

【导师】 唐林；

【作者基本信息】 信阳师范学院 ， 有机化学， 2022， 硕士

【摘要】 烯烃和炔烃都是有机化学中关键的基本组成子,具有丰富易得、价格低廉等优点。此外,由于其含有不饱和碳-碳键,能顺利地发生氧化、还原、卤代、加成、聚合等各类经典反应,从而引入相应的官能团。近年来,通过烯(炔)烃双官能团化反应可以步骤经济性地引入两个目标官能团,实现分子的快速增值化,在有机合成中已经被广泛地应用。目前,过渡金属催化、光氧化还原以及电化学条件下的烯(炔)烃双官能团化反应虽然取得了巨大的成功,但是也存在一定的问题,如催化剂昂贵、反应条件苛刻、操作复杂、反应选择性低等。因此,发展绿色、高效、高选择性的烯(炔)烃双官能团化反应在有机合成化学领域仍备受关注。虽然炔烃是合成化学中最基础的反应试剂之一,但是对其所含碳-碳三键的裂解反应的研究甚少,传统的碳-碳三键裂解策略往往需要使用化学计量的有机金属试剂或强氧化剂。基于这样的研究背景,在第二章中我们探索了铜催化炔烃碳-碳三键断裂的氧苯基化反应。该反应以炔烃为模型底物,乙腈为溶剂,N-氟代双苯磺酰胺为自由基前体和芳基源,硫酸铜为催化剂,叔丁基过氧化氢为强氧化剂,氮气为反应氛围,在80℃下搅拌4小时可快速、高效地通过串联-迁移的自由基历程发生炔烃碳-碳三键断裂的双官能团化反应,从而以良好的收率以及高度的区域选择性提供一系列芳香酮目标产物。同位素实验表明,水在这一反应中发挥着重要作用。所研究的炔烃双官能团化反应具有反应条件温和、操作简单、试剂廉价易得、区域选择性高以及底物普适性广等优点。含氟有机化合物具有良好的药效学和动力学特性,被广泛应用于小分子药物中。目前的报道通过烯烃1,2-双官能团化反应来引入含氟(氟烷基)基团主要利用过渡金属催化、可见光促进以及电化学的方法来实现。尽管这些方法已经得到了广泛的发展,仍存在一些不可避免的问题,比如有些反应通常需要添加外部的过渡金属催化剂(光催化剂)、相应配体或者电化学装置,导致反应条件苛刻且操作复杂,这在一定程度上限制了其进一步的合成应用。基于这一研究背景,在第三章中我们探索了可见光促进无外加光催化剂的烯烃多氟烷基烯基化反应。该反应以1,2-二氯乙烷为溶剂,2-苯胺基-1,4-苯醌为模型底物和光敏剂,全氟碘代丁烷为氟源,碳酸铯为碱,氮气为反应氛围,在室温条件下通过可见光照射20小时可高效地发生烯烃全氟烷基烯基化反应,以良好的收率以及高度的区域选择性提供一系列多氟烷基化的萘醌类产物。所开发的烯烃双官能团化反应具有操作简单、条件温和、试剂廉价易得和底物范围广泛等优点,更为重要的是,该反应无需外加光催化剂。更多还原

【Abstract】 Alkenes and alkynes,as important synthons in organic chemistry,have the advantages of abundant availability and low price.In addition,because they contain unsaturated carbon-carbon bonds,various classical reactions such as oxidation,reduction,halogenation,addition,and polymerization can smoothly take place,thereby introducing corresponding functional groups.In recent years,the difunctionalization of alkenes(alkynes)can economically introduce two target functional groups in one step and rapidly construct the value-added molecules,which has been widely used in organic synthesis.At present,despite remarkable achievement obtained in transition metal-catalyzed,visible light-promoted and electrochemical difunctionalization of alkenes(alkynes),these methods generally involve expensive catalysts,harsh reaction conditions,complicated operation,and low reaction selectivity.Therefore,the development of green,efficient and highly selective difunctionalization of alkenes(alkynes)still attracts much attention in the field of organic synthetic chemistry.Although alkynes are one of the most basic reagents in synthetic chemistry,reactions for the cleavage of the carbon-carbon triple bonds are rarely demonstrated.Traditionally,the cleavage of the carbon-carbon triple bonds requires stoichiometric organometallic reagents or strong oxidants.Based on this research background,we explore the copper-catalyzed oxyphenylation of alkynes through carbon-carbon triple bond cleavage in Chapter 2.The difunctionalization of alkynes can be rapidly and efficiently carried out at 80 °C for 4 hours via a tandem-migration radical process with alkynes as model substrate,acetonitrile as solvent,N-fluorobisbenzenesulfonamide as free radical precursor and aryl source,copper sulfate as catalyst,tert-butyl hydroperoxide as oxidant,and nitrogen as reaction atmosphere,providing a series of the desired aromatic ketones.Isotopic experiments show that water plays an important role in this reaction.The developed alkyne difunctionalization has the advantages of mild reaction conditions,simple operation,use of cheap and readily available reagents,high regioselectivity,and broad substrate scope.Because of good pharmacodynamics and kinetic properties,fluorinated organic compounds are prevalently applied as small molecule drugs.Existing reports of1,2-difunctionalization of alkenes for the introduction of fluorine-or fluoroalkyl-containing groups mainly rely on transition metal catalysis,photoredox and electrochemistry.Although these methods have been widely developed,they still suffer from some limitations.For example,the reactions usually require external transition metal catalysts(photocatalysts),corresponding ligands or electrochemical devices,resulting in harsh reaction conditions and complicated operations,which restricts their further synthetic applications to a certain extent.In his context,we explore visible light-promoted perfluoroalkylalkenylation of alkenes without external photocatalysts in Chapter 3.The perfluoroalkylalkenylation can be efficiently carried out at room temperature for 20 hours with 1,2-dichloroethane as solvent,2-anilino-1,4-benzoquinone as model substrate and photosensitizer,perfluoroiodobutane as fluorine source,cesium carbonate as base,and nitrogen as reaction atmosphere,providing a variety of perfluoroalkylated naphthoquinonesin good yields and excellent regioselectivity.The developed alkene difunctionalization features simple operation,mild conditions,use of cheap and readily available reagents,and a wide range of substrates.More importantly,the reaction does not require external photocatalysts.更多还原