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Enantioselective Photoorganocatalytic Synthesis of 1,4-Dicarbonyl Compounds
摘要: Stereocontrolled Synthesis of 1,4-Dicarbonyl Compounds by Photochemical Organocatalytic Acyl Radical Addition to Enals
关键词: dicarbonyls,enals,asymmetric catalysis,iminium ion activation,acyl radicals,photocatalysis
更新于2025-09-19 17:15:36
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Preparation and Characterization of Water-soluble ZnSe: Fe/ZnSe Quantum Dots
摘要: A chiral phosphoric acid-catalyzed kinetic resolution and desymmetrization of para-quinols operating via oxa-Michael addition was developed and subsequently subjected to mechanistic study. Good to excellent s-factors/enantioselectivities were obtained over a broad range of substrates. Kinetic studies were performed, and DFT studies favor a hydrogen bonding activation mode. The mechanistic studies provide insights to previously reported chiral anion phase transfer reactions involving chiral phosphate catalysts in combination with boronic acids.
关键词: directed reactivity,oxa-Michael addition,kinetics,asymmetric catalysis,chiral phosphoric acid,reaction mechanisms
更新于2025-09-11 14:15:04
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Concurrent Asymmetric Reactions Combining Photocatalysis and Enzyme Catalysis: Direct Enantioselective Synthesis of 2,2-Disubstituted Indol-3-ones from 2-Arylindoles
摘要: The combination of photoredox and enzymatic catalysis for the direct asymmetric one-pot synthesis of 2,2-disubstituted indol-3-ones from 2-arylindoles through concurrent oxidization and alkylation reactions is described. 2-Arylindoles can be photocatalytically oxidized to 2-arylindol-3-one with subsequent enantioselective alkylation with ketones catalyzed by wheat germ lipase (WGL). The chiral quaternary carbon center at C2 of the indoles was directly constructed. This mode of concurrent photobiocatalysis provides a mild and powerful strategy for one-pot enantioselective synthesis of complex compounds. The experiments proved that other lipases containing structurally analogous catalytic triad in the active site also can catalyze the reaction in the same way. This reaction is the first example of combining the non-natural catalytic activity of hydrolases with visible-light catalysis for enantioselective organic synthesis and it does not require any cofactors.
关键词: photochemistry,enzymes,heterocycles,synthetic methods,asymmetric catalysis
更新于2025-09-10 09:29:36