Study of Environmentally Friendly Organic Synthesis Based on High Pressure Reactions

1.在高压/无溶剂条件下低活性二烯的Diels-桤木反应：高压/无溶剂条件对噻吩的Diels桤木反应有显著影响。在非常相似的条件下，进行了呋喃的domino-和pincer-Diels-桤木反应。所有这些加合物不容易通过其他方法制备。从原子经济性的观点来看，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，在高压/无溶剂条件下发展了几种重要的官能团转化方法。例如，通过异硫氰酸酯和氨基吡啶之间的缩合来合成吡啶-硫脲缀合物，酮的缩醛化，通过三氯乙基氨基甲酸酯与胺的缩合来合成取代的脲，使用芳香酮/芳香胺的Strecker反应 关于我们 3.在水热条件下通过酮的缩合合成氮杂环的新方法：在热氯化铵水溶液中环酮的环化缩合以良好的产率得到完全取代的吡啶衍生物。另一方面，邻苯基苯胺盐酸盐与环酮在热水中处理，以良好的产率产生菲啶衍生物。这些都是水热化学在有机合成中的新用途的典型例子，有助于环境友好的有机合成的发展。4.在D20中水热条件下的芳香族H-D交换反应：通过在D2 O中水热条件下进行反应，开发了芳香胺的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：合成了手性吡咯烷-吡啶共轭碱催化剂，并将其应用于酮与硝基烯烃的不对称Michael加成反应。结果表明，该催化剂具有良好的催化活性、非对映选择性和对映选择性。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配体，用于L-脯氨酸催化的不对称Aldol反应。该方法的实用性举例说明了短合成的产卵引诱信息素，sphyngosines，boronoprene在光学纯的形式。7.杂项有机官能团的转换：顺式/陷阱异构化的4-取代的环己基苯衍生物，液晶材料，在TfOH的催化下。少

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