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Oxidative Palladium(II) Catalysis: A Highly Efficient and Chemoselective Cross-Coupling Method for Carbon-Carbon Bond Formation under Base-Free and Nitrogenous-Ligand Conditions

机译:氧化钯(II)催化:在无碱和氮配体条件下形成碳-碳键的高效且化学选择性的交叉偶联方法

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摘要

We report herein the development of a general and mild protocol of oxygen promoted Pd(II) catalysis resulting in the selective cross-couplings of alkenyl- and arylboron compounds with various olefins. Unlike most cross-coupling reactions, this new methodology works well even in the absence of bases, consequently averting undesired homo-couplings. Nitrogen-based ligands including dimethyl-phenanathroline enhance reactivities and offer a highly efficient and stereoselective methodology to overcome challenging substrate limitations. For instance, oxidative palladium(II) catalysis is effective with highly substituted alkenes and cyclic alkenes, which are known to be incompatible with other known catalytic conditions. Most examined reactions progressed smoothly to completion at low temperatures and in short times. These interesting results provide mechanistic insights and utilities for a new paradigm of palladium catalytic cycles without bases.
机译:我们在此报告了氧促进的Pd(II)催化的一般和温和规程的发展,从而导致烯基和芳基硼化合物与各种烯烃的选择性交叉偶联。与大多数交叉耦合反应不同,这种新方法即使在没有碱基的情况下也能很好地发挥作用,因此避免了不希望的同质耦合。包括二甲基菲咯啉在内的基于氮的配体提高了反应活性,并提供了一种高效且立体选择性的方法来克服具有挑战性的底物限制。例如,氧化钯(II)催化对于高度取代的烯烃和环状烯烃是有效的,这些烯烃和环状烯烃已知与其他已知的催化条件不相容。大多数检查过的反应在低温短时间内顺利进行至完成。这些有趣的结果为无碱钯催化循环的新范例提供了机械学见识和实用性。

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