六元含氮芳杂环烷基盐的不对称不氢化-有机化学专业毕业论文.docx

六元含氮芳杂环烷基盐的不对称氢化ABSTRACT 六元含氮芳杂环烷基盐的不对称氢化 ABSTRACT Though great progress has been made in asymmetric hydrogenation of aromatics，the reduction of pyridinols and pyrazines remains much unexplored．The N-alkyl salt activation strategy is employed to study the asymmetric hydrogenation of pyridin-3一ols，pyrrolo[1，2一口]- pyrazines and simple pyrazines in this dissertation． Piperidin-3一ones are important intermediates for the synthesis of natural products and pharmaceutical agents．The chemoselective hydrogenation of 2一and 4-substituted 3-hydroxy． pyridinium salts has been realized using[Ir(COD)CI]2／PPh3，affording piperidin．3一ones with high yields．The mild reaction conditions，hi曲chemoselectivity and easy scalability make this catalytic system highly practical．When chiral ligand is used，racemic ketones are still obtained for the 3-hydroxypyridinium salts，which is possibly due to a fast en01．ketone isomerization． Based on previous studies，a series of 6-substituted 3-hydroxypyridinium salts are synthesized and asymmetically hydrogenated，which represents scarce example on the asymmetric hydrogenation of aromatics bearing hydroxyl group．For the substituent being not adjacent to the hydroxyl group，the side reaction constructing racemic stereogenic center is avoided．The trans 6-substituted piperidin．3．oIs are obtained as the main products with up to 95％ee．Direct oxidation of the hydrogenation products give chiral piperidin．3一ones，which are easily reduced tO the c／s 6-substituted piperidin一3-ols with K-selectride． Chiral 1,2，3，4一tetrahydropyrrolo[1，2-a]pyrazines represent a class of structurally intriguing heterocycles with a broad spectrum of biological activities．The asymmetric hydrogenation of pyrrolo[1，2一a]pyrazinium salts has been realized using iridium catalyst and substrate activation strategy,providing a facile route to chiral 1,2，3，4-tetrahydropyrrolo- [1,2一a]pyrazines with up to 95％ee．The key feature of the reaction is the addition of cesium carbonate，which increases the