Iron-Catalyzed Reductive Cross-Coupling of Alkyl Electrophiles with Olefins.
Iron-Catalyzed Reductive Cross-Coupling of Alkyl Electrophiles with Olefins.
复制标题
铁催化烷基亲电子试剂与烯烃的还原交叉偶联。
DOI：
10.1002/anie.202306663
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Fu,GregoryC
中科院分区：
文献类型：
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作者：
Tong,Xiaoyu;Yang,Ze-Peng;DelAngelAguilar,CarlosE;Fu,GregoryC
就其丰度和最小毒性而言，铁相对于其他过渡金属具有优势。虽然烷基-烷基键的构建是有机合成的核心，但铁催化的烷基-烷基偶联的例子相对较少。在这里，我们报道了一种铁催化剂，它实现了烷基亲电分子的交叉偶联反应，其中在氢硅烷存在的情况下，使用烯烃来代替烷基金属试剂。碳-碳键的形成在室温下进行，该方法使用了商业上可获得的组分(Fe(OAc)2、Xantphos和Mg(OEt)2)；有趣的是，这组试剂可以直接应用于烯烃的一种独特的氢化功能化-氢硼化。机理研究与烷基亲电试剂生成烷基自由基以及碳-碳键形成之前的基本步骤(烯烃与铁结合和β迁移插入)的可逆性是一致的。
In terms of its abundance and its minimal toxicity, iron has advantages relative to other transition metals. Although alkyl–alkyl bond construction is central to organic synthesis, examples of iron‐catalyzed alkyl–alkyl couplings of alkyl electrophiles are relatively sparse. Herein we report an iron catalyst that achieves cross‐coupling reactions of alkyl electrophiles wherein olefins, in the presence of a hydrosilane, are used in place of alkylmetal reagents. Carbon–carbon bond formation proceeds at room temperature, and the method employs commercially available components (Fe(OAc)2, Xantphos, and Mg(OEt)2); interestingly, this set of reagents can be applied directly to a distinct hydrofunctionalization of olefins, hydroboration. Mechanistic studies are consistent with the generation of an alkyl radical from the alkyl electrophile, as well as with reversibility for elementary steps that precede carbon–carbon bond formation (olefin binding to iron and β‐migratory insertion).