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Updated: May 28, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Stereoselective Intramolecular Oxypalladation of Cyclic 1,3-Dione-Tethered Alkynes
Lakshmi Revati Magham1,2, Abdus Samad1,2, Anandarao Munakala1
1Department of Organic Synthesis & Process Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500007, India.
Abstract:
An unconventional, highly stereoselective, and regioselective intramolecular oxypalladation/acyloxylation cascade of alkyne-tethered cyclic 1,3-diones has been developed. This atom-economic Pd(II)-catalyzed annulation reaction is initiated by the oxypalladation of alkyne with an internal carbonyl group via 5-exo-dig cyclization instead of the conventional acetoxypalladation pathway. In this process, the carboxylic acid plays a pivotal role in the generation of an active cationic Pd-complex and the subsequent acyloxylation and proto-demetalation steps. Additionally, this method enables asymmetric cyclization using a chiral bidentate BOX ligand, achieving enantiomeric ratios of ≤93:7.
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