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Studies On Nickel-catatyzed C-C Bond Activation And Deearboxylative Cycloaddition Reactions

Posted on:2014-01-07Degree:DoctorType:Dissertation
Country:ChinaCandidate:M SunFull Text:PDF
GTID:1221330398468298Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
Selective C-C bond activation (cleavage) by transition metal complexes and decarboxylative cycloaddition of alkene are two of the most challenging subjects in organometallic chemistry. This is due not only to its fundamental seicentific interest, but also its potential utility in organic synthesis.In chapter1, the history and the development of C-C bond activation (cleavage) by transition metal complexes were summaried. Many chemists have devised a variety of strategies for C-C bond activation and significant progress has been made in this field over the past few decades. Especially, this chapter focused on two mechanism and two different strategies in C-CN bond cleavage, which may provide further research to achieve C-C bond activation.In chapter2, we have developed a highly efficient protocol for the preparation of various diphenylphosphory ligands through nickel-catalyzed C-CN bond cleavage. The cross-coupling C-P bond was achieved with the condition of NiCl2(PPh3)2,t-BuOK and Me3SiPPh2. The availability of the substrates and the remarkable scope observed make this method attractive to synthetic chemists.In chapter3, alkene difunctionalization, the addition of two functional groups across a double bond, exemplifies a class of reactions with significant synthetic potential. This emerging area examines recent developments of palladium-catalyzed difunctionalization reactions, with a focus on mechanistic strategied that allow for functionalizaiton of a common palladium alkyl intermediate.In chapter4, we have developed a novel nickel-catalyzed decarboxylative cycloaddition of alkenes with isatoic anhydrides, which provide a new method to synthesize quinolone derivatives. Nickel (0) catalyst generated in situ from NiCl2(PMe3)2and activated Zn powder is found to be very important to ensure the success of the reaction.
Keywords/Search Tags:Nickel, C-CN bond activation, decarboxylative cycloaddition, difunctionalization
PDF Full Text Request
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