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Study of Environmentally Friendly Organic Synthesis Based on High Pressure Reactions

基于高压反应的环保有机合成研究

基本信息

批准号：
14204072
负责人：
KOTSUKI Hiyoshizo
金额：
$ 35.94万
依托单位：
Kochi University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

1.Diels-Alder Reaction of Less Reactive Dienes under High-Pressure/Solvent Free Conditions :Dramatic effects of high-pressure/solvent-free conditions were recognized for the Diels Alder reaction of thiophene. Under the very similar conditions, domino- and pincer-Diels-Alder reactions of furan were performed. All of these adducts were not easily prepared by other means. From the viewpoint of atom economy these provide a unique method in organic synthesis.2.Uncatalyzed Functional Group Transformations under High-Pressure/Solvent-Free Conditions :Several important methods for the functional group transformations were developed under high-pressure/solvent-free conditions in the absence of any catalysts. For example, the synthesis of pyridine-thiourea conjugates via condensation between isothiocyanates and aminopyridines, acetalization of ketones, synthesis of substituted ureas via condensation of trichloroethylcarbamates with amines, Strecker reaction using aromatic ketones/aromatic amines … More / trirnethylsilyl cyanide.3.Novel Synthesis of Nitrogen Heterocycles via Condensation of Ketones under Hydrothermal Conditions :Cyclocondensation of cyclic ketones in hot aqueous ammonium chloride gave fully substituted pyridine derivatives in good yields. On the other hand, treatment of o-phenylaniline hydrochloride salts with cyclic ketones in hot water produced phenanthridine derivatives in good yields. These are all typical examples of novel use of hydrothermal chemistry in organic synthesis and contribute to the development of environmentally friendly organic synthesis.4.Aromatic H-D Exchange Reactions under Hydrothermal Conditions in D20 :The efficient method for H-D exchange reactions of aromatic amines was developed by conducting the reactions in D2O under hydrothermal conditions.5.Development of Novel Asymmetric Organocatalysts :Novel synthesis of chiral pyrrolidine-pyridine conjugate base catalysts was performed, and these catalysts were applied for the asymmetric Michael addition reaction of ketones with nitroolefins. The results were excellent in view of catalytic activity, diastereoselectivity, and enantioselectivity.6.Organocatalytic Asymmetric Synthesis of Natural Products :Novel straight chain aliphatic aldehyde synthons were developed for the use in L-proline catalyzed asymmetric aldol reactions. The utility of this method was exemplified by the short synthesis of oviposition attractant pheromone, sphyngosines, boronolide in optically pure forms.7.Miscellaneous Organic Functional Group Transformations:Cis/traps isomerization of 4-substituted cylohexylbenzene derivatives, liquid crystalline materials, under the catalysis of TfOH. Less

1.高压/无溶剂条件下反应性较低的二烯的狄尔斯-阿尔德反应：高压/无溶剂条件对噻吩的狄尔斯-阿尔德反应具有显着影响。在非常相似的条件下，进行了呋喃的多米诺骨牌反应和钳式狄尔斯-阿尔德反应。所有这些加合物都不容易通过其他方法制备。从原子经济性的角度来看，这为有机合成提供了一种独特的方法。2.高压/无溶剂条件下的非催化官能团转化：在没有任何催化剂的情况下，开发了在高压/无溶剂条件下官能团转化的几种重要方法。例如，异硫氰酸酯与氨基吡啶缩合合成吡啶硫脲缀合物、酮缩醛化、氨基甲酸三氯乙酯与胺缩合合成取代脲、芳香酮/芳香胺的Strecker反应……更多/三甲基甲硅烷基氰化物。通过酮在水热条件下缩合生成氮杂环：环酮在热氯化铵水溶液中环缩合，以良好的收率得到完全取代的吡啶衍生物。另一方面，在热水中用环酮处理邻苯基苯胺盐酸盐以良好的收率产生菲啶衍生物。这些都是水热化学在有机合成中的新型应用的典型例子，为环境友好型有机合成的发展做出了贡献。4.D20中水热条件下的芳香族H-D交换反应：通过在D2O中水热条件下进行反应，开发了芳香胺H-D交换反应的有效方法。5.新型不对称有机催化剂的开发：手性化合物的新型合成制备了吡咯烷-吡啶共轭碱催化剂，并将该催化剂应用于酮与硝基烯烃的不对称迈克尔加成反应。催化活性、非对映选择性和对映选择性均取得了优异的结果。6.天然产物的有机催化不对称合成：开发了新型直链脂肪醛合成子，用于L-脯氨酸催化的不对称羟醛反应。该方法的实用性通过光学纯形式的产卵引诱剂信息素、鞘氨醇、硼酸硼内酯的短合成得到例证。7.其他有机官能团转化：在TfOH的催化下，4-取代的环己基苯衍生物、液晶材料的顺式/陷阱异构化。较少的