以碳为中心的自由基与烯酰胺的分子间加成反应。一种合成全取代α-碘代烯酰胺的区域和立体选择性途径。
Intermolecular Addition of Carbon-Centered Radicals to Ynamides. A Regio- and Stereoselective Route to Persubstituted α-Iodo-enamides.
作者信息
Dwadnia Nejib, Lingua Hugo, Mouysset Dominique, Mimoun Liliane, Siri Didier, Bertrand Michèle P, Feray Laurence
机构信息
Aix Marseille Univ, CNRS, ICR, Institut Chimie Radicalaire, UMR 7273, Equipes CMO et CT, Campus St Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France.
出版信息
J Org Chem. 2020 Mar 20;85(6):4114-4121. doi: 10.1021/acs.joc.9b03255. Epub 2020 Mar 2.
Rather surprisingly, C-C bond formation through "intermolecular" radical addition to internal ynamides has never been reported. Actually, ynamides are excellent acceptors for "electrophilic" carbon-centered radicals. These processes enable the introduction of functionalized alkyl chains at Cβ, groups that have not yet been introduced via the addition of organometallics. Radical carboiodination affords persubstituted α-iodo-enamides in moderate to high yield. The addition is totally stereoselective. Theoretical support to the mechanism and the scope and limitation of the reaction are discussed.
相当令人惊讶的是，通过“分子间”自由基加成到内炔酰胺上形成碳 - 碳键的反应从未被报道过。实际上，炔酰胺是“亲电”碳中心自由基的优良受体。这些过程能够在Cβ位引入官能化的烷基链，而通过有机金属试剂加成尚未引入过这些基团。自由基碳碘化反应能以中等至高收率得到全取代的α - 碘代烯酰胺。该加成反应具有完全的立体选择性。文中讨论了该反应机理的理论支持以及反应的范围和局限性。
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