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Palladium/Norbornene-Catalyzed ortho Aliphatic Acylation with Mixed Anhydride: Selectivity and Reactivity
Organic Letters ( IF 5.2 ) Pub Date : 2018-01-05 00:00:00 , DOI: 10.1021/acs.orglett.7b03514
Shibo Xu 1 , Julong Jiang 1 , Linlin Ding 1 , Yao Fu 1 , Zhenhua Gu 1
Affiliation  

A palladium/norbornene-catalyzed ortho acylation for the efficient synthesis of functionalized alkyl aryl ketones is reported. Studies on the electronic and steric properties of mixed aryl anhydrides indicated that the cross-coupling favored with the electron-enriched aryl acyl group. DFT calculation on the oxidative addition of Pd(II) with 2,4,6-(Cl)3C6H2CO2C(O)Ph suggested that 2,4,6-(Cl)3C6H2C(O)–O bond cleavage was more kinetically disfavored than that of the PhC(O)–O bond by 11.7 kJ/mol.

中文翻译:

钯/降冰片烯催化的混合脂肪族邻位脂肪酰化反应:选择性和反应性

报道了钯/降冰片烯催化的邻位酰化,用于有效合成官能化的烷基芳基酮。对混合的芳基酸酐的电子和空间特性的研究表明,交叉偶联有利于富电子的芳基酰基。用2,4,6-(Cl)3 C 6 H 2 CO 2 C(O)Ph氧化Pd(II)的DFT计算表明2,4,6-(Cl)3 C 6 H 2 C (O)–O键的断裂在动力学上比PhC(O)–O键的断裂更不利于11.7 kJ / mol。
更新日期:2018-01-05
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