掌握钯催化的交叉偶联反应：原位预催化剂还原设计的关键作用。

IF 4.6 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2025-01-22 DOI:10.1039/d4qo02335h

Tommaso Fantoni, Chiara Palladino, Riccardo Grigolato, Beatrice Muzzi, Lucia Ferrazzano, Alessandra Tolomelli, Walter Cabri

{"title":"掌握钯催化的交叉偶联反应：原位预催化剂还原设计的关键作用。","authors":"Tommaso Fantoni, Chiara Palladino, Riccardo Grigolato, Beatrice Muzzi, Lucia Ferrazzano, Alessandra Tolomelli, Walter Cabri","doi":"10.1039/d4qo02335h","DOIUrl":null,"url":null,"abstract":"Palladium catalyzed cross coupling reactions are among the most used methods for carbon-carbon bond formation in the agrochemical and pharmaceutical segments. The key step common to all methodologies based on Pd(0) catalysis is the generation in situ of the active catalyst. The paper describes how to control pre-catalysts reduction in order to generate the target complex species avoiding phosphine oxidation or, as in the case of the Heck-Cassar-Sonogashira and the Suzuki-Miyaura reactions, reactants consumption via dimerization. For PPh3, DPPF, DPPP, Xantphos, SPhos, RuPhos, XPhos and sSPhos we identified protocols able to maximize the reduction via alcohol preserving ligands and reagents. The correct combination of counterion, ligand, and base allowed to perfectly control the Pd(II) reduction to Pd(0) in the presence of primary alcohols.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":4.6000,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mastering Palladium Catalyzed Cross-Coupling Reactions: The Critical Role of In Situ Pre-catalyst Reduction Design.\",\"authors\":\"Tommaso Fantoni, Chiara Palladino, Riccardo Grigolato, Beatrice Muzzi, Lucia Ferrazzano, Alessandra Tolomelli, Walter Cabri\",\"doi\":\"10.1039/d4qo02335h\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Palladium catalyzed cross coupling reactions are among the most used methods for carbon-carbon bond formation in the agrochemical and pharmaceutical segments. The key step common to all methodologies based on Pd(0) catalysis is the generation in situ of the active catalyst. The paper describes how to control pre-catalysts reduction in order to generate the target complex species avoiding phosphine oxidation or, as in the case of the Heck-Cassar-Sonogashira and the Suzuki-Miyaura reactions, reactants consumption via dimerization. For PPh3, DPPF, DPPP, Xantphos, SPhos, RuPhos, XPhos and sSPhos we identified protocols able to maximize the reduction via alcohol preserving ligands and reagents. The correct combination of counterion, ligand, and base allowed to perfectly control the Pd(II) reduction to Pd(0) in the presence of primary alcohols.\",\"PeriodicalId\":97,\"journal\":{\"name\":\"Organic Chemistry Frontiers\",\"volume\":\"2 1\",\"pages\":\"\"},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2025-01-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4qo02335h\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4qo02335h","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}

引用次数: 0

摘要

钯催化的交叉偶联反应是农业化学和制药领域最常用的碳-碳键形成方法之一。基于Pd(0)催化的所有方法的共同关键步骤是活性催化剂的原位生成。本文描述了如何控制预催化剂的还原，以产生目标络合物，避免磷化氢氧化，或者在Heck-Cassar-Sonogashira和Suzuki-Miyaura反应的情况下，通过二聚化消耗反应物。对于PPh3， DPPF， DPPP, Xantphos, SPhos, RuPhos， XPhos和sSPhos，我们确定了能够通过醇保存配体和试剂最大化还原的方案。在伯醇存在的情况下，对离子、配体和碱的正确组合可以完美地控制Pd（II）还原为Pd(0)。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Mastering Palladium Catalyzed Cross-Coupling Reactions: The Critical Role of In Situ Pre-catalyst Reduction Design.

Palladium catalyzed cross coupling reactions are among the most used methods for carbon-carbon bond formation in the agrochemical and pharmaceutical segments. The key step common to all methodologies based on Pd(0) catalysis is the generation in situ of the active catalyst. The paper describes how to control pre-catalysts reduction in order to generate the target complex species avoiding phosphine oxidation or, as in the case of the Heck-Cassar-Sonogashira and the Suzuki-Miyaura reactions, reactants consumption via dimerization. For PPh3, DPPF, DPPP, Xantphos, SPhos, RuPhos, XPhos and sSPhos we identified protocols able to maximize the reduction via alcohol preserving ligands and reagents. The correct combination of counterion, ligand, and base allowed to perfectly control the Pd(II) reduction to Pd(0) in the presence of primary alcohols.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.