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Transition Metal-Catalyzed Cyclization Ketoxime Acetates/Enamines For The Synthesis Of Azaheterocycles

Posted on:2017-05-17Degree:DoctorType:Dissertation
Country:ChinaCandidate:M N ZhaFull Text:PDF
GTID:1311330512963973Subject:Organic Chemistry
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The thesis is mainly focused on coupling/cyclization reaction for the preparation of azines?pyrroles?pyridines and isoquinolines. The content mainly includes the following two parts:The first part involves transition metal-catalyzed homocoupling of oximes or cyclization of ketoxime acetates with DMF/tertiary anilines. The second part presents coupling of enamides with alkynes?arynes or nitroolefins for the synthesis of multisubstituted pyrroles?pyridines and isoquinolines.Part?.Oximes and their derivatives are versatile synthetic building blocks in organic synthesis. Chapter 1 summarized the recent progress in transition metal-catalyzed coupling reactions of oximes. Chapter 2 presented a facile and efficient copper-catalyzed homocoupling of oximes for the synthesis of azines. This transformation involved N-O bond cleavage and N-N bond formation. Chapter 3 exhibited a novel Ru-catalyzed cyclization of ketoxime carboxylates with DMF for the synthesis of tetrasubstituted symmetrical pyridines. A methyl carbon on DMF performed as a source of a one carbon synthon in the reaction. Chapter 4 displayed an unprecedented Fe-catalyzed cyclization of ketoxime carboxylates and N,N-dialkyl anilines for the synthesis of 2,4-disubstituted and 2,4,6-trisubstituted pyridines. The methylene carbon on N,N-dialkyl anilines functioned as a source of one-carbon synthon in the reaction.Part ?.Enamides and their derivatives are a class of powerful building blocks in organic synthesis. Chapter 1 introduced the synthetic methods of enamides and summarized the recent progress in transition-metal-catalyzed oxidative coupling/annulations of enamides. Chapter 2 exhibited a novel and general method for Cu-catalyzed coupling of enamides with alkynes for the synthesis of functionalized pyridines. The chemistry was allowed to extend to coupling of enamides and arynes for the synthesis of substituted isoquinolines under transition metal-free conditions. Chapter 3 described a copper-promoted oxidative coupling of enamides with electron-deficient alkynes for the synthesis of multisubstituted NH pyrroles. Chapter 4 presented a palladium-catalyzed alkenyl C-H activation annulation of aryl enamides with alkynes for the synthesis of triaryl-substituted pyrroles. Chapter 5 showed an efficient tandem one-pot protocol for the synthesis of highly functionalized NH pyrroles based on FeCl3-catalyzed addition and cyclization of Blaise reaction intermediates and nitroolefins. And in Chapter 6, in connection with our interest in carbonylation, we have developed a novel palladium-catalyzed carbonylation of indoles with CO and aromatic boronic acids for the synthesis of indol-3-yl aryl ketones.
Keywords/Search Tags:ketoximes, enamines, transition-metal catalyst, coupling/cyclization reaction, azaheterocycles
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