【作者】 毕海鹏；

【导师】 梁永民； 李朝军；

【作者基本信息】 兰州大学 ， 有机化学， 2010， 博士

【摘要】 第一章：在第一章中,系统的总结了各类脱羧反应的发展和在有机合成中的应用。根据反应种类的不同,我们分别从以下五个方面进行了详细的阐述：(1)过渡金属催化的脱羧—质子化反应；(2)过渡金属催化的脱羧-aldol类型的加成反应；(3)过渡金属催化的脱羧—烷基化反应；(4)过渡金属催化的其他类型的各种脱羧反应；(5)过渡金属催化的脱羧环化反应；(6)过渡金属催化的脱羧偶联反应。第二章：在第二章中,首先介绍了我们小组最近几年对于各种碳环化反应的研究。然后,详细的介绍了在钯催化条件下,使用炔丙基化合物和2-碘苯酚类,通过串联反应高区域选择性的合成四环化合物的方法。并且在反应过程中,Pd(0)先后参与了两次不同的催化循环,这在以前的报道中是非常少见的。第三章：在第三章中,我们首先简单介绍了传统的丙二稀化合物的合成方法。其次,详细的介绍了钯/碳催化的使用炔丙基化合物高区域选择性的合成茚的衍生物的方法。反应条件简单易行,在空气/室温条件下便可进行,并且使用了非常少的催化剂。反应的产物也可以很方便的应用于其他的钯催化的环化反应中。第四章：在第四章中,我们详细的介绍了使用炔丙基化合物高区域、高立体选择性的合成各种茚和苯并呋喃的方法。在反应过程中,我们发现分子间的亲核进攻优于分子内的亲核进攻顺序,这一新颖的亲核进攻顺序在以往的类似反应中是不多见的。第五章：在第五章中,我们简单介绍了合成各种含有杂原子的脱羧偶联反应,之后我们又详细的介绍了CuBr催化的分子间的脱羧偶联反应。该反应使用a-氨基酸为底物,在中性条件下通过构建了不同的碳-碳键(Csp3-Csp3, Csp3-Csp2 and Csp3-Csp)合成了一系列含有各种官能团的含氮化合物。第六章：在第六章中,我们简单介绍了我们小组之前报道的A3反应和CDC反应,然后详细的介绍了醛／酮促进的铜催化的脱羧偶联反应。在反应过程中,仅仅生成了CO2和H2O两种副产物,同时观察到了非常有趣的区域选择性。通过对共振中间体相对稳定性的理论化学计算,合理解释了这种有趣的区域选择性。第七章：在第七章中,我们详细的介绍了铁催化的分子间的脱羧偶联反应。该反应使用a-氨基酸作为原料,通过构建Csp3-Csp2的方式合成了一系列在有机合成中有潜在使用价值的配体(同时含有三级胺和萘酚)。第八章：在第八章中,我们详细的介绍了近些年来通过亲电环化反应构建碳-氧键,碳-氮键,碳-碳键以及其他碳-杂键的各种方法。然后详细介绍了通过亲电环化反应高区域、高立体选择性的合成茚和萘的方法。通过此方法得到的碘代产物可以很方便的应用于一些钯催化的反应中。更多还原

【Abstract】 Chapter 1.In chapter 1, development and application of decarboxylation reactions in organic synthesis were summarized in detail. According to the different reaction types, we facilitated a detailed description from six aspects.(1) transition-metal-catalyzed decarboxylative protonation;(2) transition-metal-catalyzed decarboxylative aldol-addition reaction;(3) transition-metal-catalyzed decarboxylative alkylation;(4) transition-metal-catalyzed other types of decarboxylation reaction;(5) transition-metal-catalyzed decarboxylative cyclization;(6) transition-metal-catalyzed decarboxylative coupling.Chapter 2.In chapter 2, some recent research results about carboannulation of our group were summaried. And a novel Pd-catalyzed intermolecular tandem reaction of propargylic compounds with 2-iodophenols for the synthesis of tetracyclic compounds with sequential high regioselectivity was described in detail. In addition, the present process is one of the comparatively few examples in which a Pd(0) catalyst is simultaneously involved in two catalytic cycles.Chapter 3.In chapter 3, we briefly introduced the traditional method of preparing allenes firstly. And then, a novel Pd/C-catalyzed reaction for the synthesis of indene derivatives from propargylic compounds with high regioselectivity was described in detail. And this reaction was run under ambient conditions of temperature and air. It is noteworthy that lower catalyst loadings were used in this process. The resulting products can be further elaborated using Pd-catalyzed annulation reactions.Chapter 4. In chapter 4, we descried a novel Pd-catalyzed carboannulation of propargyl compounds with high regio-and stereoselectivity in detail. In these processes, indene and benzo[b]furan derivatives are synthesized and a novel sequence of nucleophilic attack is observed, which intermolecular nucleophilic attack is prior to the intramolecular reaction.Chapter 5.In chapter 5, we presented the recent development of transition-metal-catalyzed decarboxylative coupling for the systhsis of compound including heteroatom. And then, we descried a novel CuBr-catalyzed intermolecular decarboxylative Csp3-Csp3, Csp3-Csp2 and Csp3-Csp coupling reaction using a-amino acids as starting materials under neutral conditions. This catalytic reaction would be an efficient method for the synthesis of various functionalized nitrogen-containing compounds.Chapter 6.In chapter 6, we briefly introduced the A3 reaction and CDC reaction that we reported before. And then, we described an interesting aldehyde-and ketone-induced carboxylation-coupling reaction catalyzed by copper providing CO2 and H2O as the only byproducts. In these processes, interesting regioselectivities were observed. Such regioselectivities were explained by the relative stability of proposed resonance structures based on computation methods.Chapter 7.In chapter 7, we presented in detail a novel iron-catalyzed intermolecular decarboxylative Csp3-Csp2 coupling reaction using a-amino acids as starting materials. In this process, a broad range of potential ligands (tertiary amino-naphthol) for organic syntheses was obtained easily.Chapter 8.In chapter 8, we described in detail the constructions of C-O bond, C-N bond, C-C bond and other bonds through electrophilic cyclization reaction in recent years. And then, we descried an electrophilic cyclization reaction. In these progresses, Indene or naphthalene derivatives are readily prepared with high regio-and stereoselectivity. The resulting iodine-containing products are readily elaborated to more complex products by using known organopalladium chemistry.更多还原