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Aryl Fluoride Activation through Palladium–Magnesium Bimetallic Cooperation: A Mechanistic and Computational Study
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-06-22 , DOI: 10.1021/acscatal.0c01301 Chen Wu 1 , Samuel P McCollom 1 , Zhipeng Zheng 1 , Jiadi Zhang 1 , Sheng-Chun Sha 1 , Minyan Li 1 , Patrick J Walsh 1 , Neil C Tomson 1
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-06-22 , DOI: 10.1021/acscatal.0c01301 Chen Wu 1 , Samuel P McCollom 1 , Zhipeng Zheng 1 , Jiadi Zhang 1 , Sheng-Chun Sha 1 , Minyan Li 1 , Patrick J Walsh 1 , Neil C Tomson 1
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Herein is described a mechanistic study of a palladium-catalyzed cross-coupling of aryl Grignard reagents to fluoroarenes that proceeds via a low-energy heterobimetallic oxidative addition pathway. Traditional oxidative additions of aryl chlorides to Pd complexes are known to be orders of magnitude faster than with aryl fluorides, and many palladium catalysts do not activate aryl fluorides at all. The experimental and computational studies outlined herein, however, support the view that at elevated Grignard/ArX ratios (i.e., 2.5:1), a Pd–Mg heterobimetallic mechanism predominates, leading to a remarkable decrease in the energy required for Ar–F bond activation. The heterobimetallic transition state for the C–X bond cleavage is proposed to involve simultaneous Pd backbonding to the arene and Lewis acid activation of the halide by Mg to create a low-energy transition state for oxidative addition. The insights gained from this computational study led to the development of a phosphine ligand that was shown to be similarly competent for Ar–F bond activation.
中文翻译：
通过钯-镁双金属合作活化芳基氟化物：机理和计算研究
本文描述了通过低能异双金属氧化加成途径进行的钯催化的芳基格氏试剂与氟代芳烃的交叉偶联的机理研究。已知传统的芳基氯化物向Pd络合物的氧化加成要比芳基氟化物快几个数量级，而且许多钯催化剂根本不活化芳基氟化物。然而，本文概述的实验和计算研究支持以下观点：格利雅/ ArX比升高（即2.5：1）时，Pd-Mg异双金属机制占主导地位，导致Ar-F键所需的能量显着降低激活。提出了用于C–X键断裂的异双金属过渡态涉及同时将Pd背键连接到芳烃上，以及Mg激活卤化物的路易斯酸，从而为氧化加成创造出低能过渡态。从这项计算研究中获得的见识导致了膦配体的发展，该配体被证明具有类似的Ar-F键活化能力。
更新日期：2020-07-17
中文翻译：
通过钯-镁双金属合作活化芳基氟化物：机理和计算研究
本文描述了通过低能异双金属氧化加成途径进行的钯催化的芳基格氏试剂与氟代芳烃的交叉偶联的机理研究。已知传统的芳基氯化物向Pd络合物的氧化加成要比芳基氟化物快几个数量级，而且许多钯催化剂根本不活化芳基氟化物。然而，本文概述的实验和计算研究支持以下观点：格利雅/ ArX比升高（即2.5：1）时，Pd-Mg异双金属机制占主导地位，导致Ar-F键所需的能量显着降低激活。提出了用于C–X键断裂的异双金属过渡态涉及同时将Pd背键连接到芳烃上，以及Mg激活卤化物的路易斯酸，从而为氧化加成创造出低能过渡态。从这项计算研究中获得的见识导致了膦配体的发展，该配体被证明具有类似的Ar-F键活化能力。
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