Studies On Transition Metal Catalyzed Decarboxylation And Electrophilic Cyclization

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.