Enantioselective Synthesis of α-Oxygenated Ketones via Organocatalytic Formal O–H Bond Insertion of Sulfonium Ylides
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Described here is an example of organocatalytic enantioselective formal O–H bond insertion of α-carbonyl sulfur ylides, providing efficient access to highly enantioenriched ketones bearing a tertiary α-oxygenated stereocenter. This metal-free approach is complementary to the well-established metal-based diazo carbonyl chemistry, which has gained broad success for esters but not for ketones. The proper choice of a chiral thiourea catalyst in combination with N -hydroxyl phthalimides proved to be crucial to success. Mechanistic studies indicate that the reaction is likely initiated by activation of sulfonium ylides by hydrogen bonding, thus distinct from previous related cases using chiral phosphoric acid catalysis that involves initial protonation of the basic sulfonium ylide functionality. DFT studies provided important insights into the key C–O bond-forming intermediates and transition states.
DOI: 10.1021/jacs.5c10842
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G1162233175, Organocatalytic Asymmetric Construction of All-Carbon Quaternary Stereocenters in Congested Systems, G1678791140, Design of Chiral Catalysts and Organocatlytic Processes for Asymmetric Synthesis, Development of New Strategies for the Asymmetric Synthesis of α-Chiral Carbonyl Compounds, Chiral Phosphoric Acid-Catalyzed Asymmetric Electrochemical Transformations, Regioselective and Stereoselective Addition of Ynones and Siloxy Alkynes, G534716927, G637631384
OpenAlex ID: W4413350733