Synthesis of flexible bis-phosphines and application to Pd-catalyzed aminocarbonylation of alkenes with primary aryl amines with aid of H2O-additive

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-03-22 DOI:10.1016/j.molstruc.2025.142127

Yu-Fen Xie , Guang-Hui Shi , Guo-Sheng Zhang , Long-Gen Hu , Xiao-Li Zhao , Yong Lu , Ye Liu

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引用次数: 0

Abstract

The efficiency of Pd-catalyzed aminocarbonylation of alkenes for straight-forward synthesis of amides is highly dependent on the stereoelectronic properties of the involved ligands. Herein, three kinds of bis-phosphines (L1-L3), which were featured with flexibility by introduction of rotatory methylene-unit, were synthesized and applied to the Pd-catalyzed aminocarbonylation of alkenes and L1 with suitable flexibility could develop a convenient trans-P,P-chelation to Pd-center to afford a stable complex of Pd(L1)Cl₂ with a typical square-planar configuration. It was found that without the presence of auxiliary acid-additive, L1-modified Pd(MeCN)₂Cl₂ system [or Pd(L1)Cl₂] exhibited the remarkable catalytic activity and excellent regioselectivity (99 %) for the aminocarbonylation of styrene (derivatives) with aniline (derivatives), with isolated yields of 54–87 % for the branched amides. H₂O-additve played a pivotal role in boosting the performance of L1-Pd(MeCN)₂Cl₂ catalyst as a requisite hydrogen source for the in situ formation of HCl, which served as an acid-additive to initiate the generation of the catalytic active palladium-hydride intermediate.

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.