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Hydroacylation Reaction Of Azodicarboxylate And Formation Of Fully Substituted Hexahydro-isoindolinones Derivatives

Posted on:2017-03-17Degree:DoctorType:Dissertation
Country:ChinaCandidate:H B ZhangFull Text:PDF
GTID:1221330503962820Subject:Chemistry
Abstract/Summary:PDF Full Text Request
Synthesis of natural and unnatural biologically active molecules, pharmaceutical compounds and radical hydroacylation reaction of azodicarboxylate via Br?nsted-acid catalysis is studied in this thesis. This paper includes five parts:Part 1: This part introduced hydroacylation reaction firstly, then hydroacylation reaction of azodicarboxylate and cooperative catalysis were described. The recent advances of applications of transition-metal, ionic liquid and water in this field were also covered. In the end of this chapter, we described merging of Lewis acid catalysis and Br?nsted acid catalysis in organic chemistry.Part 2: The C-H bond activation and formation of the C–N bond are one of the most important transformations in organic synthesis that have wide applications in the synthesis of numerous natural and unnatural biologically active molecules. One subclass of these efficient reactions using azodicarboxylates as electrophiles has caused a considerable amount of interest. Cooperative catalysis has emerged as one of the most stimulating, dynamic and synthetically powerful areas in contemporary organic synthesis, while Lewis acid catalysis and Br?nsted acid catalysis represent two fundamental activation modes in organic synthesis. We have developed an efficient hydroacylation reaction of aldehydes and azodicarboxylates employing the strategy of merging Lewis- and Br?nsted- acid catalysis, which is from simple substrates. Merging these two modes could improve the applicability and the rate of this reaction. As far as we know, there is no report about the mechanism of free radical in this reaction.Part 3: This part introduced organocatalytic multi-component cascade reactions and quadruple cascade reactions. The key point is that bifunctional tertiary amine thioureas have emerged as powerful catalysts for promoting a wide array of useful organocascade sequences and quadruple cascade reactions.Part 4: Isoindolines and their analogues are one kind of the most widespread compounds in nature. They feature not only high biological activity, but also diverse chemical properties. Synthesis of fully substituted hexahydro-isoindolinones is very difficult due to the steric hindrance and the high strain of the molecular architectures. A new and efficient synthetic method to get fully substituted hexahydro-isoindolinones is developed using bifunctional tertiary amine thioureas as powerful catalysts. To the best of our knowledge, there is no efficient synthetic method developed toward fully substituted hexahydro-isoindolinones so far. The products are obtained in good yield and diastereoselectivity. This structure was first reported. The one-pot cascade quadruple protocol features easily available starting materials, simple manipulation, mild conditions and atom-economy.Part 5: C-C bond cleavage has become an important method in the field of organic synthesis, especially the ring opening reaction of the cyclopropane has become an important research direction, and attracted many research group’s interest. The chemical bond energy of cyclopropane and cyclobutane are similar. So we design the a series of reactions, using vinyl cyclopropane and cyclobutane as substrate, metal catalyst and organic catalyst will be combined together, tried to make the exploration of the new reaction. Although there is no success, but for this kind of catalytic model and an insight into the nature of the substrate, lay the foundations for the later response to explore.
Keywords/Search Tags:hydroacylation, cooperative catalysis, formation of the C–N bond, tertiary amine thioureas, quadruple cascade, one-pot, fully substituted hexahydro-isoindolinones, vinylcyclopropane, cyclobutane
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