Jingjun Huang, Dang Binh Ho, Gregory Gaube, Holly Celuszak, Joseph Becica, Gilian T. Thomas, Nathan D. Schley, David C. Leitch
{"title":"用于氧化加成络合物形成和高周转催化反应的热稳定性无烯钯源","authors":"Jingjun Huang, Dang Binh Ho, Gregory Gaube, Holly Celuszak, Joseph Becica, Gilian T. Thomas, Nathan D. Schley, David C. Leitch","doi":"10.1021/acs.organomet.4c00125","DOIUrl":null,"url":null,"abstract":"Oxidative addition complexes play a crucial role in Pd-catalyzed transformations. They are not only key catalytic intermediates but also powerful and robust precatalysts, and effective reactants for late-stage functionalization of complex molecules. However, accessing a given oxidative addition complex is often challenging due to a lack of effective and stable palladium sources with the correct reactivity. Herein, we report an easily prepared and bench-stable Pd(II) dialkyl complex, <sup>DMP</sup>DAB–Pd–BTSM (<sup>DMP</sup>DAB = <i>N</i>,<i>N</i>′-bis(2,6-<u>d</u>i<u>m</u>ethyl<u>p</u>henyl)<u>d</u>i<u>a</u>za<u>b</u>utadiene; BTSM = <u>b</u>is(<u>t</u>rimethyl<u>s</u>ilyl<u>m</u>ethyl)), that is a versatile precursor for generating Pd(II) oxidative addition complexes and is highly active as a Pd source for <i>in situ</i> catalyst formation in cross-coupling reactions. A crucial aspect of this structure is the absence of alkene-based stabilizing ligands common to other Pd precursors. We demonstrate the utility of this precursor in the formation of several Pd(II) complexes, including phosphine and diimine-ligated oxidative addition complexes, and in high-turnover-number catalysis of C–O, Suzuki, and Heck coupling reactions.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A Thermally Stable, Alkene-Free Palladium Source for Oxidative Addition Complex Formation and High-Turnover Catalysis\",\"authors\":\"Jingjun Huang, Dang Binh Ho, Gregory Gaube, Holly Celuszak, Joseph Becica, Gilian T. Thomas, Nathan D. Schley, David C. Leitch\",\"doi\":\"10.1021/acs.organomet.4c00125\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Oxidative addition complexes play a crucial role in Pd-catalyzed transformations. They are not only key catalytic intermediates but also powerful and robust precatalysts, and effective reactants for late-stage functionalization of complex molecules. However, accessing a given oxidative addition complex is often challenging due to a lack of effective and stable palladium sources with the correct reactivity. Herein, we report an easily prepared and bench-stable Pd(II) dialkyl complex, <sup>DMP</sup>DAB–Pd–BTSM (<sup>DMP</sup>DAB = <i>N</i>,<i>N</i>′-bis(2,6-<u>d</u>i<u>m</u>ethyl<u>p</u>henyl)<u>d</u>i<u>a</u>za<u>b</u>utadiene; BTSM = <u>b</u>is(<u>t</u>rimethyl<u>s</u>ilyl<u>m</u>ethyl)), that is a versatile precursor for generating Pd(II) oxidative addition complexes and is highly active as a Pd source for <i>in situ</i> catalyst formation in cross-coupling reactions. A crucial aspect of this structure is the absence of alkene-based stabilizing ligands common to other Pd precursors. We demonstrate the utility of this precursor in the formation of several Pd(II) complexes, including phosphine and diimine-ligated oxidative addition complexes, and in high-turnover-number catalysis of C–O, Suzuki, and Heck coupling reactions.\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-05-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.organomet.4c00125\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00125","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
A Thermally Stable, Alkene-Free Palladium Source for Oxidative Addition Complex Formation and High-Turnover Catalysis
Oxidative addition complexes play a crucial role in Pd-catalyzed transformations. They are not only key catalytic intermediates but also powerful and robust precatalysts, and effective reactants for late-stage functionalization of complex molecules. However, accessing a given oxidative addition complex is often challenging due to a lack of effective and stable palladium sources with the correct reactivity. Herein, we report an easily prepared and bench-stable Pd(II) dialkyl complex, DMPDAB–Pd–BTSM (DMPDAB = N,N′-bis(2,6-dimethylphenyl)diazabutadiene; BTSM = bis(trimethylsilylmethyl)), that is a versatile precursor for generating Pd(II) oxidative addition complexes and is highly active as a Pd source for in situ catalyst formation in cross-coupling reactions. A crucial aspect of this structure is the absence of alkene-based stabilizing ligands common to other Pd precursors. We demonstrate the utility of this precursor in the formation of several Pd(II) complexes, including phosphine and diimine-ligated oxidative addition complexes, and in high-turnover-number catalysis of C–O, Suzuki, and Heck coupling reactions.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.