Dicarbonyl Metal Carbene: A Versatile Synthetic Tool for C-H Functionalization, Formal [3+2] Cycloaddition and Enantioselective Cyclopropanation
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Yuan, Shaoren
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Abstract
In recent decades, dicarbonyl diazo-derived metal-carbenes have been heavily focused on synthetic organic chemistry due to their versatile reactivity that allows the synthesis of a wide variety of compounds. This thesis discussed the study of two types of dicarbonyl diazo compounds within three characteristic reaction categories. The first category involves the use of indolyl-α-diazo-β-ketoesters and enol ethers which, under the catalysis of Cu(II), are converted into dihydrofuran (DHF) acetals via [3+2] cycloaddition. These DHF acetals are subsequently utilized in the synthesis of multi-substituted carbazoles. In the second category, N-aryl-α-diazo-β-amidoesters are used as reagents for the benzylic C(sp3)−H alkylation of methyl-substituted arenes, with distinct selectivity outcomes being observed under the influence of two different Rh(II) carboxylates catalysts. The final category reveals the successful application of N-aryl-α-diazo-β-amidoesters compounds in the enantioselective cyclopropanation of a broad range of olefins, catalyzed by a novel chiral Rh(II) carboxylate.
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2023-12-15
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Dissertation