Palladium-Catalyzed C-H Functionalization of Acyldiazomethane and Tandem Cross-Coupling Reactions.
Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consist...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 13; pp. 4435 - 4445 |
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| Autores principales: | , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
4/8/2015
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=102711944&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 102711944 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/8/2015 vid: 137 iid: 13 pid: 997 pub: American Chemical Society artinfo: ui: 102711944 10.1021/ja513275c ppf: 4435 ppct: 10 formats: tig: atl: Palladium-Catalyzed C-H Functionalization of Acyldiazomethane and Tandem Cross-Coupling Reactions. aug: au: Fei Ye Shuanglin Qu Lei Zhou Cheng Peng Chengpeng Wang Jiajia Cheng Lokman Hossain, Mohammad Yizhou Liu Yan Zhang Zhi-Xiang Wang Jianbo Wang affil: Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China su: Palladium Aryl iodides Molecular shapes Density functional theory Catalytic activity sug: subj: Palladium Aryl iodides Molecular shapes Density functional theory Catalytic activity ab: Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through AgCO assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol). pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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