通过铜介导的无张力酮的脱酰基化反应进行烯丙基化。
Olefination via Cu-Mediated Dehydroacylation of Unstrained Ketones.
机构信息
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
出版信息
J Am Chem Soc. 2021 Dec 8;143(48):20042-20048. doi: 10.1021/jacs.1c09587. Epub 2021 Nov 22.
Abstract
The dehydroacylation of ketones to olefins is realized under mild conditions, which exhibits a unique reaction pathway involving aromatization-driven C-C cleavage to remove the acyl moiety, followed by Cu-mediated oxidative elimination to form an alkene between the α and β carbons. The newly adopted '-methylpicolinohydrazonamide (MPHA) reagent is key to enable efficient cleavage of ketone C-C bonds at room temperature. Diverse alkyl- and aryl-substituted olefins, dienes, and special alkenes are generated with broad functional group tolerance. Strategic applications of this method are also demonstrated.
摘要
酮的脱酰基化反应在温和条件下实现，其具有独特的反应途径，涉及芳构化驱动的 C-C 断裂以去除酰基部分，然后在 Cu 介导的氧化消除作用下，在α和β碳原子之间形成烯烃。新采用的'-甲基 picolinohydrazonamide (MPHA) 试剂是在室温下实现酮 C-C 键高效断裂的关键。各种烷基和芳基取代的烯烃、二烯和特殊烯烃都具有广泛的官能团容忍度。该方法的战略应用也得到了证明。
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