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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Palladium-Catalyzed Cyclization/Sulfonylation Enabling Access to 2-Pyrrolidinone-Functionalized Allylic Sulfones
Qing Li1,2, Ying Tian1, Ya-Nan Jia1
1Department of Chemistry, Capital Normal University, Beijing 100048, China.
Abstract:
An efficient Pd-catalyzed cyclization/sulfonylation reaction of N-allylbromoacetamides with Na2S2O4 and allyl esters via "SO2" insertion has been developed, enabling the first synthesis of 2-pyrrolidinone-functionalized allylic sulfones. In this protocol, inexpensive and readily available Na2S2O4 functions dually as a sulfur dioxide source and a single-electron donor, thereby sustaining the catalytic cycle. The reaction exhibits a broad substrate scope and excellent tolerance to diverse functional groups, affording a wide range of allylic sulfones with exclusive (E) selectivity. Mechanistic studies suggest a reaction pathway involving intramolecular radical cyclization, the insertion of "SO2," and subsequent allylic substitution of a π-allyl-Pd(II) intermediate in a single reaction.
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