Photoinduced Copper-Catalyzed Enantioselective Allylic C(sp3)–H Oxygenation of Acyclic Terminal Olefins Enabled by SphenBOX
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Although the copper-catalyzed allylic C(sp 3 )–H oxygenation (Kharasch–Sosnovsky reaction) is a powerful transformation known for over a half century, its enantioselective version has been developed with drawbacks. High enantioselectivity was not achieved for acyclic terminal olefins and tertiary C–H bonds. Here we have addressed these long-standing challenges enabled by the design of new SphenBOX ligands. When combined with photocatalysis, a range of valuable allylic esters can be obtained directly from terminal olefins and carboxylic acids with high efficiency, regioselectivity, and enantioselectivity. Unprecedented enantioconvergent oxygenation of allylic tertiary C(sp 3 )–H bonds is demonstrated, allowing construction of quaternary stereocenters with high enantioselectivity. Structural analysis indicates that SphenBOX features a compact chiral pocket that may contribute to its superior performance.
DOI: 10.1021/jacs.5c06136
Authors: Xu-Kuan Qi, Qiang Dai, Yangyi Gu, Kwan Shing Lau, Herman H. Y. Sung, Ian D. Williams, Zhenyang Lin, Chaoshen Zhang, Jianwei Sun
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, G2949869024, Development of New Organocatalytic Asymmetric Processes, Chiral Phosphoric Acid-Catalyzed Asymmetric Electrochemical Transformations, G4227328392, G534716927, G637631384
OpenAlex ID: W4411138411