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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Palladium-Catalyzed Intramolecular Asymmetric Allylic Amidation: A General Route to 5-Substituted Chiral Oxazolines
1State Key Laboratory of Natural Product Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, China.
Abstract:
A general and modular catalytic enantioselective route to 5-substituted chiral oxazolines has been developed via palladium-catalyzed intramolecular asymmetric allylic amidation. This strategy employs readily available racemic 2-substituted-5-styryl oxazolidinones as substrates. Key to the success is the identification of a sterically hindered biphenol-derived phosphoramidite ligand, which, in combination with Pd2(dba)3, promotes the cyclization with high efficiency and enantiocontrol. The reaction demonstrates broad substrate scope and excellent functional group tolerance, accommodating a wide range of sterically diverse 2-substituents and electronically varied aryl allylic units, delivering the desired 5-vinyl oxazolines in good yields with high enantioselectivity (up to 99% ee).
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