Compatibility Score for Rational Electrophile Selection in Pd/NBE Cooperative Catalysis.
Compatibility Score for Rational Electrophile Selection in Pd/NBE Cooperative Catalysis.
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DOI：
10.1016/j.chempr.2020.09.004
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发表时间：
2020-10-08
期刊：
影响因子：
23.5
通讯作者：
Liu P
中科院分区：
文献类型：
--
作者：
Qi X;Wang J;Dong Z;Dong G;Liu P
提出了一种机理指导的方法来预测钯/顺丁烯二酸（Pd/NBE）协同催化芳基卤的ipso/ortho双官能化反应中亲电试剂的相容性。这些反应中的关键挑战是鉴定在催化循环中的单独氧化加成事件中与不同过渡金属络合物选择性反应的正交亲电试剂和芳基卤化物起始材料。我们进行了详细的实验和计算机制的研究，以确定催化活性的Pd（II）中间体和底物依赖的机制与各种类型的碳和氮亲电试剂的反应。引入亲电试剂相容性评分（ECS）的概念，根据亲电试剂和卤代芳烃对Pd（0）和Pd（II）配合物的正交反应性，合理选择亲电试剂。该方法被应用于预测亲电体的相容性在Pd/NBE合作催化与各种亲电耦合合作伙伴用于烷基化，芳基化，胺化，和酰化反应。开发使用容易获得的起始材料形成新型键的催化方法一直是有机合成的长期目标。虽然传统的交叉偶联反应发生在亲核试剂和亲电试剂之间，但最近出现了涉及两种不同亲电试剂的各种偶联反应。这些反应提供了有前途的平台，合成功能化的分子，考虑到各种各样的商业上可获得的碳和杂原子亲电试剂。然而，识别彼此相容的亲电试剂并不简单，因为它们必须具有正交反应性，使它们能够在催化循环的不同基本步骤中选择性地与不同的有机金属物质反应。在这里，我们描述了一种机械引导的方法来合理地预测亲电体，满足这些标准，并可以潜在地用于多亲电体偶联反应。提出了一种预测Pd/NBE协同催化中有效亲电体的机理指导方法。计算和实验机制的研究表明，阴离子芳基-乙酰基-钯（ANP）的催化活性物种。这些见解是用来建立一个计算程序，以快速预测芳基卤化物和亲电子试剂之间的相容性，通过评估其正交反应在Pd（0）/（II）和Pd（II）/（IV）氧化加成步骤。
A mechanistically guided approach is developed to predict electrophile compatibility in the palladium/norbornene (Pd/NBE) cooperative catalysis for the ipso/ortho difunctionalization of aryl halides. A key challenge in these reactions is to identify orthogonal electrophile and aryl hali de starting materials that react selectively with different transition metal complexes in separate oxidative addition events in the catalytic cycle. We performed detailed experimental and computational mechanistic studies to identify the catalytically active Pd(II) intermediate and the substrate-dependent mechanisms in reactions with various types of carbon and nitrogen electrophiles. We introduced the concept of electrophile compatibility score (ECS) to rationally select electrophiles based on the orthogonal reactivity of electrophile and aryl halide towards the Pd(0) and Pd(II) complexes. This approach was applied to predict electrophile compatibility in the Pd/NBE cooperative catalysis with a variety of electrophilic coupling partners used in alkylation, arylation, amination, and acylation reactions. Developing catalytic methods for novel types of bond formation using readily available starting materials has been a long-term goal in organic synthesis. While traditional cross-coupling reactions take place between a nucleophile and an electrophile, various coupling reactions involving two different electrophiles have recently emerged. These reactions provide promising platforms for synthesizing functionalized molecules, considering the large variety of commercially available carbon and heteroatom electrophiles. However, it is not trivial to identify electrophiles that are compatible with each other, because they must have orthogonal reactivity that allows them to react selectively with different organometallic species in different elementary steps of the catalytic cycle. Here, we describe a mechanistically guided approach to rationally predict electrophiles that meet these criteria and can be potentially used in multi-electrophile coupling reactions. A mechanistically guided approach is developed for predicting effective electrophiles in Pd/NBE cooperative catalysis. Computational and experimental mechanistic studies revealed an anionic aryl-norbornyl-palladacycle (ANP) as the catalytically active species. These insights are used to establish a computational procedure to rapidly predict compatibility between aryl halides and electrophiles by evaluating their orthogonal reactivity in the Pd(0)/(II) and Pd(II)/(IV) oxidative addition steps.
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