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Updated: Jan 9, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Friedel-Crafts acylation via interrupted Beckmann fragmentation of activated ketones
Ye Ji Shin1, Eswaran Kamaraj1, Hee Nam Lim1
1Department of Chemistry, Yeungnam University 280 Daehak-Ro Gyeongsan Gyeongbuk 38541 Republic of Korea heenam@yu.ac.kr.
Abstract:
Friedel-Crafts (FC) acylation has long been a fundamental electrophilic arene substitution reaction. In this work, we report a new procedure for FC acylation utilizing stable and user-friendly acylium precursors, α-oximinoketones. The key to this methodology is the selective Csp2 -Csp2 bond cleavage in α-oximinoketones, facilitated by triflic anhydride, leading to the formation of acylium ions under mild conditions. This approach demonstrates compatibility with a variety of substituted alkyl, (hetero)aryl ketones, and cyclic ketones as acylating reagents, where cyclic ketones allow for unique ring-opening FC acylation without relying on ring strain. DFT calculations confirmed the mechanistic pathway, highlighting the generation of acylium ions via the selective Beckmann fragmentation over Beckmann rearrangement.
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