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钯催化脂肪族烯烃有氧均偶联生成二烯：限速协同金属化-去质子化的证据

Palladium-catalyzed aerobic homocoupling of aliphatic olefins to dienes: evidence for rate-limiting concerted metalation-deprotonation.

作者信息

Van Minnebruggen Sam, Poels-Ryckeboer Harry, Van Dessel Hendrik, Martens Frederick, Stuyck Wouter, Nelis Tom, Beckers Igor, Bugaev Aram, De Vos Dirk

机构信息

Centre for Membrane Separations, Adsorption, Catalysis and Spectroscopy for Sustainable Solutions (cMACS), KU Leuven 3001 Leuven Belgium

SuperXAS Beamline, Paul Scherrer Institute 5232 Villigen Switzerland.

出版信息

Chem Sci. 2024 Dec 9;16(6):2573-2580. doi: 10.1039/d4sc06686c. eCollection 2025 Feb 5.

DOI:10.1039/d4sc06686c
PMID:39677937
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11638970/
Abstract

Palladium(ii)-catalyzed dehydrogenative coupling of aliphatic olefins would enable an efficient route to (conjugated) dienes, but remains scarcely investigated. Here, 2-hydroxypyridine (2-OH-pyridine) was found to be an effective ligand for Pd(ii) in the activation of vinylic C(sp)-H bonds. While reoxidation of Pd(0) is challenging in many catalytic oxidations, one can avoid in this reaction that the reoxidation becomes rate-limiting, even under ambient O pressure, by working in coordinating solvents. kinetic studies the elementary steps governing this reaction were elucidated, resulting in enhanced performance (turnover frequency) of the Pd(ii)/2-OH-pyridine system. The diene product is formed a consecutive activation of two olefins on the same Pd atom, followed by a β-hydride elimination. The first olefin activation, the C-H activation, determines the overall reaction rate under these conditions. The catalytic complex was studied by ESI-MS and X-ray absorption spectroscopy, revealing that the coordination sphere of the working palladium complex contains two 2-OH-pyridine ligands.

摘要

钯（II）催化的脂肪族烯烃脱氢偶联反应将为制备（共轭）二烯烃提供一条有效途径，但目前对此研究甚少。在此，发现2-羟基吡啶（2-OH-吡啶）是钯（II）活化烯基C（sp）-H键的有效配体。虽然在许多催化氧化反应中，将Pd（0）再氧化具有挑战性，但在该反应中，通过在配位溶剂中进行反应，即使在环境氧气压力下，也可以避免再氧化成为限速步骤。动力学研究阐明了控制该反应的基本步骤，从而提高了Pd（II）/2-OH-吡啶体系的性能（周转频率）。二烯烃产物是通过在同一钯原子上连续活化两个烯烃，然后进行β-氢化物消除而形成的。在这些条件下，第一次烯烃活化，即C-H活化，决定了总反应速率。通过电喷雾电离质谱（ESI-MS）和X射线吸收光谱对催化配合物进行了研究，结果表明，工作钯配合物的配位球包含两个2-OH-吡啶配体。

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