【作者】 赵连彪；

【导师】 王进贤； 胡雨来；

【作者基本信息】 西北师范大学 ， 有机化学， 2003， 硕士

【摘要】 有机锌试剂是最早发现的有机金属试剂之一，但由于其低的反应活性，在有机合成中一直未得到很好应用然而近年来的研究表明，在Lewis酸的催化下，将有机锌试剂用过渡金属的盐或络合物转换为相应的有机过渡金属试剂后可与多种亲电试剂发生反应，而且有机锌试剂可通过锌与卤代烃的氧化插入反应方便地得到，试剂中可允许有多种官能团存在，从而把其所携带的官能团不经特殊保护即可直接引入到目标分子中，因而大大缩短了合成路线，引起了有机化学家的广泛关注。 大量的文献表明，有机卤化锌的活性低于二烷基锌试剂。在大多数情况下，有机卤化锌的反应都是在等量毒性较大的铜盐CuCN／2LiCl存在下进行的此外，对苄基型的卤化锌试剂却没有引起人们的足够重视，因而我们选择了采用微波辐射来促进带官能团的苄基卤化锌试剂与芳酰氯、α—硝基芳基乙烯等亲电试剂的反应，得到了较好的结果，扩大了微波辐射技术在有机金属试剂反应中的应用，进一步拓展了带官能团的有机卤化锌试剂的应用范围。 本论文共分五章。 第一章：带官能团的有机卤化锌试剂在有机合成中的研究进展 本章主要对有机锌试剂，特别是带官能团的有机卤化锌试剂的产生、发展、制备及其在有机合成中的应用作了详细的综述。 第二章：微波辐射下Pd（Ⅱ）配合物催化带官能团的苄基卤化锌与芳酰氯的偶联反应研究 本章首次将微波辐射技术用于Pd（PPh₃）₂Cl₂催化下带官能团的苄基卤化锌与芳酰氯的偶联反应中。通过实验考察了原料配比、溶剂、微波辐射功率、辐射时间等多种因素对该偶联反应的影响。用微波辐射来促进有机卤化锌试剂的反应活性，避免了使用毒性很强的CuCN／2LiCl盐将有机锌试剂转化为活性较高的有机铜试剂，进一步拓展了低活性有机卤化锌试剂及微波在有机合成化学中的研究范围。提出了一种快速、简便、高产率合成二芳基乙酮类化合物的新方法。参考相关文献及实验提出了可能的反应机理。合成了10个二芳基乙酮类化合物。 第三章：微波辐射下带官能团的苄基卤化锌与1-硝基-2-芳基乙烯的取代反应研究 本章首次将微波辐射技术用于带官能团的苄基卤化锌与α—硝基芳基乙烯的反应中。我们发现乙酰丙酮镍催化或无催化剂（产率稍低）条件下微波辐射都能促使带官能团的节基卤化锌快速取代Q一硝基芳基乙烯中的硝基。澎丈实验考察了原料配比、溶剂、微波辐射功率、辐射时间等多种因素对该反应的影响。扩大了有机卤化锌试剂在微波有机合成（MORE）化学中的研究和应用。提出了一种快速、简便、高产率合成二芳基丙烯类化合物的新方法。 第四章:Pd（工I）配合物催化带官能团的节基卤化锌与芳香醛的烯基化反应研究 在三甲基氯硅烷存在下，Zmol%的Pd（即h3）2C12催化带官能团的节基卤化锌与芳香醛发生了烯基化反应生成了二芳基乙烯类化合物。当无三甲基氯硅烷存在时，带官能团的节基卤化锌与芳香醛发生了Pd（PPh3）:Cl:催化的加成取代反应生成了二芳基乙醇类化合物。实验发现Pd（工I）配合物催化下的烯基化反应同Ni（工I）、比（I）络合物催化下的这类反应一样，具有高的区域选择性和立体选择性，新的C=C键在芳香醛拨基碳原子和节基卤化锌试剂中与锌原子相连的碳原子之间形成。节基卤化锌试剂及芳香醛的芳环上所带的官能团（氯、澳、轻基等）都可被直接引入到加成消除产物中。且反应的产率高于Ni（工I）、伪（I）络合物催化下的同类反应。利用此法合成了十个芳基取代的a一芳基乙烯类化合物，并通过现代波谱分析表征了产物结构。 第五章:微波辐射下Pd（工1）配合物催化四苯硼钠与节基型卤化物的偶联反应研究 碳一碳键的形成反应是有机合成中非常重要的一类反应。加zuki偶联反应是非常有用的CsPZ一CspZ键形成反应，由于有机硼试剂良好的热稳定性、耐水、耐氧性而受到有机化学家的广泛关注。 本章首次将微波辐射技术应用于Pd（PPh3）2C12催化的NaBPh;与节基型卤化物的偶联反应中，实现了有机硼试剂与sp3杂化碳的偶联，扩大了suzuki偶联反应的研究领域。同时采用MW工一PTC联用，以水为溶剂实现了一种生态友好的绿色合成途径。j面丈实验分别考察了原料配比月豁d、微波辐射功率、车蒯‘时间等多种因素对该偶联反应的影响。从而优选出较佳的反应条件，合成了十个不对称二芳基甲烷化合物。郑恿过现代波谱分析表征了其结构。此反应方法具有很好的化学选择性，操作简便，收率好，反应迅速等特点。更多还原

【Abstract】 The applications of organozinc reagent in organic synthesis have been limited for a long time although it is one of the earliest prepared organometallics. The reason is that it is inactive towards most of electrophiles except Refonnatsky reagent. However, investigation in recent years shows that the organozinc reagent can react with a range of electrophiles in the presence of a Lewis acid and by the catalysis of transition metal complex or salts. Mort importantly, a variety of organozinc halides (RZnX) can be conveniently obtained by the oxidative insertion of zinc into R-X and they can tolerate a wide range of functionalities such as carbonyl, ester, halide and cyano group. These functional groups can be directly introduced into target molecules. And possibly a shorter synthetic route would be realized by avoiding the use of protection-deprotection steps as well as functional group interconversions.Although its application in organic synthesis has extended rapidly, a survey of literature shows that the reactivity of organic zinc halides are lower than diorganozincs and in most cases, they doesnt react with most electrophiles until these reagents are transmetalated to corresponding organometallic reagents by CuCN or other transition metallic salts. So in this thesis we want to use microwave irradiation which has been broadly used to accelerate organic reaction in recent years to activate the reactivity of FG-PhCHiZnX when it react with some electrophiles such as aroyl chlorides, 1 -aryl-2-nitroethenes and so on.This thesis includes five chapters.Chapter One: The Development of Polyfunctional Organozinc Halides in Organic Synthesis.In this section, the development, preparation and application of organozincs, especially the functional organozincs, are reviewed in details.Chapter Two: Palladium(II)-Catalyzed Cross Coupling Reaction of Functionalized BenzylzincHalides with Aroyl Chlorides under Microwave Irradiation.The cross coupling reactions of functionalized benzylzinc halides (FG-PhCHiZnX) witharoyl chlorides catalyzed by Pd(PPh3)2Cl2(2mol%) under microwave irradiation was first reported. The results show that when Pd(PPh3)2Cl2 as the catalyst , FG-PhCH2ZnX can smoothly coupled with aroyl chlorides under microwave irradiation to give the coupling products in excellent yields. From the viewpoint of organic synthesis methods and application of microwave in organic synthesis, this method is a new, convenient work-up, fast, and affords good yield. The reaction mechanism also proposed on the basis of experiments and the literatures. And ten products were synthesized by this procedure.Chapter Three: Study of the Substitution Reaction of Functionalized Benzylzinc Halides with a -Nitrostyrene under Microwave IrradiationIn chapter 3, a microwave- irradiated reaction of Functionalized benzyl zinc reagents with a -nitrostyrene was reported. Microwave methodology was first introduced into the reactions of Functionalized benzyl zinc reagents with 1 -aryl-2-nitroethenes. The experimental results show that nitro group of a -nitrostyrene can be rapidly substituted by functionalized benzylzinc halides (FG-PhCHiZnX) under microwave irradiation in the presence of Ni(acac)2 or in the absence of catalyst with lower yield of products. The effects of irradiation power, time, and various solvents on the reaction were investigated. We broaden the scope of the microwave application and posted a new method for synthesis of 1,3-diarylpropenes. The reactions finished in 9 or 12 minutes and with satisfactory yields. So the reaction has following advantages: rapid reaction speed, convenient manipulation and excellent yields of products.Chapter Four: Palladium(II)-Catalyzed Olefmation Reaction of Functionalized Benzylzinc Halides with Aromatic Aldehydes.In this part, a reaction of benzyl zinc halides with aromatic aldehydes catalyzed by Palladium complexes was first reported. Under the catalysis of Pd(PPh~3)2Cl2 and TMSCl, these reactions could be proceeded efficiently giving high yield of functionalized stilb更多还原