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Asymmetric PdII‐catalyzed intramolecular aminotrifluoromethoxylation of unactivated alkenes using readily accessible and stable CsOCF3 as a trifluoromethoxide source has been developed, which affords a wide variety of enantiomerically enriched β‐substituted OCF3‐containing piperidines in good yields. Introducing a sterically bulky group into pyridine‐oxazoline (Pyox) ligands is crucial to increasing...
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