康 · 学术 | Reaction of the Day No. 1027
2023-06-19
临床研究临床结果
Regio and enantioselective remote dioxygenation of internal alkenesXiaonan Li1,3, Tilong Yang2,3, Jiayuan Li1, Xiang Li1, Pinhong Chen1, Zhenyang Lin 2 & Guosheng Liu11State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, China.2Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.3These authors contributed equally: Xiaonan Li, Tilong Yang.—Nat. Chem., https://doi-org.libproxy1.nus.edu.sg/10.1038/s41557-023-01192-3Recommended by Murong Xu_ MC3KEYWORDS: enantioselective, dioxygenation, internal alkenes, palladium-catalyzed, Pyox ligandsABSTRACT: Methods for the enantioselective direct oxygenation of internal alkenes have provided chemists with versatile and powerful toolboxes for the synthesis of optically pure alcohols, one of the most privileged structural motifs. Regioselectivity, however, remains a formidable challenge in the functionalization of internal alkenes. Here we report a palladium-catalyzed highly regio- and enantioselective remote 1,n-dioxygenation (n ≥ 4) of internal alkenes with engineered pyridine-oxazoline (Pyox) ligands. The reactions proceed efficiently and exhibit a broad substrate scope with excellent regio- and enantioselectivity, affording optically pure 1,n-diol acetates as the key synthons for important bioactive molecules. Experimental studies and density functional theory calculations provide evidence that the regioselectivity is governed by the reactivity disparity of two allylic C–H bonds, where the oxypalladation is reversible and the first palladium migration step proves to be the regioselectivity-determining step, enabled by the modified phenyl-substituted Pyox ligands.Regio- and enantioselective 1,n-dioxygenation of internal alkenesThe catalytic reactions and challenges of design in catalytic remote dioxygenationRegioselective ARD reaction and ligand screening (*ARD: asymmetric remote dioxygenation)Scope of Pd-catalysed remote dioxygenation of internal alkenesSynthetic applicationsSummary and CommentsProf. Guosheng Liu and Zhenyang Lin et al have developed a palladium-catalysed method for the highly regioselective ARD reaction of internal alkenes. Described herein represents a powerful tool for the efficient synthesis of chiral 1,n-diols from simple alkenes. The concept for tuning the regioselectivity of unactivated internal alkenes was demonstrated by altering the rate-determining step, enabled by the modified Pyox ligand, which lays the groundwork for further exploration of other regioselective functionalization reactions.
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