Palladium-Catalyzed Decarbonylative Nucleophilic Halogenation of Acid Anhydrides DOI Open Access
Tian Tian,

Shuhei Uei,

Weidan Yan

и другие.

Catalysts, Год журнала: 2025, Номер 15(2), С. 191 - 191

Опубликована: Фев. 19, 2025

In this study, we developed a palladium-catalyzed decarbonylative nucleophilic halogenation reaction using inexpensive and readily available acid anhydrides as substrates. This approach effectively circumvents the instability of acyl chlorides low reactivity fluorides. The Pd/Xantphos catalyst system exhibited excellent compatibility with thermodynamically kinetically challenging reductive elimination C–X bonds (X = I, Br, Cl) from Pd(II) intermediates. Notably, for electron-donating substrates, adopting an open significantly improved efficiency. positive effect may be due to reversible nature CO insertion deinsertion, which helps direct toward desired pathway by allowing generated exit system. Mechanistic studies suggest that proceeds through highly reactive halide intermediate, followed unimolecular fragment coupling (UFC) via decarbonylation or alternative involving formation activated anionic palladate complex in presence lithium halide.

Язык: Английский

Palladium-Catalyzed Decarbonylative Nucleophilic Halogenation of Acid Anhydrides DOI Open Access
Tian Tian,

Shuhei Uei,

Weidan Yan

и другие.

Catalysts, Год журнала: 2025, Номер 15(2), С. 191 - 191

Опубликована: Фев. 19, 2025

In this study, we developed a palladium-catalyzed decarbonylative nucleophilic halogenation reaction using inexpensive and readily available acid anhydrides as substrates. This approach effectively circumvents the instability of acyl chlorides low reactivity fluorides. The Pd/Xantphos catalyst system exhibited excellent compatibility with thermodynamically kinetically challenging reductive elimination C–X bonds (X = I, Br, Cl) from Pd(II) intermediates. Notably, for electron-donating substrates, adopting an open significantly improved efficiency. positive effect may be due to reversible nature CO insertion deinsertion, which helps direct toward desired pathway by allowing generated exit system. Mechanistic studies suggest that proceeds through highly reactive halide intermediate, followed unimolecular fragment coupling (UFC) via decarbonylation or alternative involving formation activated anionic palladate complex in presence lithium halide.

Язык: Английский

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