【作者】 严文君；

【导师】 王进贤；

【作者基本信息】 西北师范大学 ， 有机化学， 2008， 硕士

【摘要】 金属促进的反应是一种很具有研究价值的反应体系,近年来,在有机合成中的应用已经成为有机化学领域中的一个新的研究热点,金属促进的反应具有条件温和,反应速度快,化学选择性、区域选择性和立体选择性都很强等优点,是一类颇具使用价值和应用前景的合成方法。近年来,随着绿色化学的兴起和发展,环境友好-经济性已成为技术创新的主要推动力,同时对绿色有机合成提出了严峻的挑战和发展机遇。发展更温和的化学合成工艺对于可持续技术是非常重要的。我们研究组从绿色化学的角度出发,首次研究并报道了一类新的反应,即无溶剂下锌粉促进的羰基化合物与卤代烃的碳碳键形成反应。论文主要研究了锌粉促进TMSX调控无溶剂下羰基化合物与卤代烃类的烯基化、硅醚化、醚化、环化反应和锌铜偶促进羰基化合物与卤代苯乙酮的Reformatsky-Aldol类反应,以及它们的反应机理。本论文共分为两章:第一章:现代羰基烯基化反应研究进展本章主要综述了现代羰基烯基化反应的主要研究进展,对各类羰基烯基化反应方法的反应的机理、立体化学问题、优点及局限性以及它们反应在有机合成中的应用进行了较为系统全面的综述。第二章:锌粉促进羰基化合物与卤代烃的碳碳键形成反应研究本章在简要综述绿色化学及锌粉促进绿色有机合成研究进展基础上,首次报道了锌粉促进TMSX调控下,羰基化合物与烯基化、硅醚化、醚化、Prins类环化反应。合成了三十四种反式烯烃,九种硅醚、七种对称醚和七种2,4,6-三取代四氢吡喃,其中包括三十一种新化合物。通过熔点、IR、¹H NMR、¹³C NMR、MS以及元素分析表征了产物结构,并研究了其反应机理。论文通过实验发现了锌粉促进TMSX调控无溶剂下羰基化合物与卤代烃的立体选择性烯基化、硅醚化、醚化以及锌铜偶促进的Prins类环化反应;提供了构建C=C,C-O和O-Si键的新方法和新途径;同时我们也考察了不同的反应条件对反应的影响并对反应条件进行了优化,推断了可能的反应机理。与目前已报道的同类方法相比,这一方法具有收率高、反应时间短、适用范围广、立体选择性强、不使用有机溶剂等优点,符合绿色化学原则,具有环境友好特点。此外,在本章第三部分实验首次设计了锌铜偶促进各种醛与卤代酮在无溶剂条件下的Reformatsky-Aldol类反应,合成了三十四种羟基酮,其中包括二十五种新化合物。通过熔点、IR、¹H NMR、¹³C NMR、MS以及元素分析表征了产物结构,并研究了其反应机理。在论文中,我们利用“一锅”、室温、无溶剂锌铜偶促进下溴代酮与各种醛羰基化合物反应的方法合成了β-羟基酮。与现在众多的Reformatsky类反应相比,该反应具有适用底物范围广,反应时间短,操作简便易行,化学选择性和区域选择性好,无需使用溶剂和催化剂,在室温下就可以达到较好的反应产率等特点。我们提供了一个环境友好、经济、清洁的方法。同时,我们也通过分析提出了本反应体系可能的反应机理——单电子转移（SET）的机理。并通过X晶体衍射对化合物3-（9-蒽基）-3-羟基-1-苯基-1-丙酮的晶体结构进行了解析,确定了单晶结构,讨论了晶体内的弱相互作用和化合物的其它性质。更多还原

【Abstract】 Metal-promoted reaction is provided with extraordinary worthiness of research as a reaction system. In recent years, the applications of Metal-promoted reaction in organic synthesis have become a new research focus. The reactions of have several advantages such as the quick speed of reaction, chemical selectivity, region selectivity and solid selectivity, so it is a kind of synthesis reagents with considerable applicable value and applicable prospect. With the rapidly emerging and development of green chemistry, environmentally friendly-economics have become an important impetus of technology innovator, and make green organic synthesis face serious challenge. Developing more benign synthetic procedures in chemical synthesis is important in moving towards sustainable technologies. our group from the view of green chemistry reported that now found the new reactions, zinc mediated carbonyl compounds with aryl or alkyl halides for carbon-carbon bonds formation reaction.The thesis mainly investigated the reaction that zinc powder mediated stereoselective olefination, silyetherization, and etherization to Prins-cyclization of carbonyl compounds with aryl or alkyl halide using the Lewis acid （TMSiX） as regular in one-pot under solvent-free conditions, andβ-hydroxy ketones through zinc-copper couple promoted aldehydes carbonyl compounds withα-bromoketones orα-bromoacetones Reformatsky-Aldol reaction in one-pot under solvent-free conditions, and we also proposed mechanism for these reaction.This thesis includes two chapters.Chapter one: The development of modern Carbonyl Olefination.This chapter summarized the recent progress in the major methodologies of carbonyl olefination, which is one of the most fundamental transformations in organic synthesis, Specifically depict and reviewed the mechanism、regio- and stereoselective problems、advantages and limitations and evolvement of variety of carbonyl olefination methods in detail and systerm.Chapter two: A Study on the Zinc Mediated Carbonyl Compounds with Aryl or Alkyl halides for Carbon-Carbon bonds Formation ReactionThis chapter the first section is base on a brief review which contains recent development of green chemistry and zinc powder mediated green organic synthesis research, we first time report olefination, silyetherization, etherization and Prins-cyclization were carried out from aromatic carbonyl compounds with aryl or alkyl halides using the Lewis acid （TMSiX） as regular mediated by zinc powder in one-pot under solvent-free conditions. Thirty-four （E）-alkene compounds, nine sily ethers, seven symmetry ethers and seven 2,4,6-trisubstituted tetrahydropyrans were synthesized using this procedure and thirty-one compounds are novel products. All products were characterized by melting point, IR, 1H NMR, 13C NMR, MS and elemental analyses, and we also investigated mechanism for these reaction.Base on the thesis experimental, We found the reaction that zinc powder mediated stereoselective olefination, silyetherization, etherization of carbonyl compounds with aryl or alkyl halide using the Lewis acid （TMSiX） as regular in one-pot under solvent-free conditions, and zinc-copper couple promoted Prins-cyclization of carbonyl compounds with aryl or alkyl halide in one-pot under solvent-free conditions. This new method offers the possibility for the formation of new C=C, C-O, O-Si bonds and the synthesis of the natural active products. At the same time, we began to focus on the different affects of varies factors on the carbonyl olefination, silyetherization, etherization and Prins-cyclization reactions were studied to afford the optimized reaction condition, and we propose the general reaction mechanism. Compared with literature methods, the valuable features of our methodology include: higher yield, shorter reaction time, broader substrate scope, good steroeselecivity and predictability, solvent-free and so on. The method accorded with green chemistry theory and illustrated friendly environment principle.Moreover, We also reported Reformatsky-Aldol reaction that zinc-copper couple promoted aldehydes carbonyl compounds withα-bromoketones orα-bromoacetones in one-pot under solvent-free conditions. Thirty-fourβ-hydroxy ketones compounds were synthesized using this procedure and twenty-five compounds are novel products. All products were characterized by melting point, IR, ¹H NMR, ¹³C NMR, MS and elemental analyses, and we also investigated mechanism for these reaction.The section in this thesis, Reformatsky-Aldol reaction induced by zinc-copper couple in one-pot under solvent-free conditions was executed for the first time. We achieved thatβ-hydroxy ketones was synthesized through zinc-copper couple promoted aldehydes carbonyl compounds withα-bromoketones orα-bromoacetones in one-pot under solvent-free conditions, and the reactions has satisfactory results. Compared with many literature methods, the valuable features of our new Reformatsky-Aldol methodology:Broader substrate scope, excellent yields, shorter reaction time, simpler operation, high chemselectivity and regiospecificity, no catalyser and solvent-free. We have developed an environmental friendly, economically viable and cleaner methodology. This reaction mechanism of single electron transfer （SET） was proposed through the analysis. The compound 3-（anthracen-10-yl）-3-hydroxy-1-phenylpropan- -1-one is characterized both by spectral methods and X-ray single crystal diffraction. The weak interactions in the crystals is discussed.更多还原