Iron-catalyzed cross-coupling of alkyl halides with alkenyl grignard reagents
Iron-catalyzed cross-coupling of alkyl halides with alkenyl grignard reagents
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DOI：
10.1002/anie.200702206
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Cossy, Janine
中科院分区：
文献类型：
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作者：
Guerinot, Amandine;Reymond, Sebastien;Cossy, Janine
乙烯基金属试剂和未活化的烷基卤化物之间的过渡金属催化的C2 H2 C键偶联是一种有用的反应[1-3]，可以使用铜，[4]钯，镍或钴络合物作为催化剂来实现。[1-3例如，伯烷基溴可以使用钯催化的Stille偶联与烯基锡试剂偶联。[6]烷基卤化物与烯基锌试剂[7]或与烯基锆物质[8]的Negishi交叉偶联反应也在钯络合物的存在下进行。最近，[Co（acac）3]（acac=乙酰丙酮化物）被用作伯和仲烷基卤化物与1-（三甲基甲硅烷基）乙烯基镁的交叉偶联反应的催化剂。[9]该反应通过自由基途径进行，并且以良好至优异的产率获得交叉偶联产物。然而，需要20至40摩尔%的钴络合物，并且不与其它烯基格氏试剂发生反应。[9]As随着可持续化学的重要性日益增长，合成有机方法越来越受到关注，铁催化的交叉偶联反应是构建C13 C键的有前途的研究领域之一，因为铁便宜且比钯、钴或镍更环保。[10在20世纪70年代高知及其同事的开创性工作之后，[12，13]直到最近，Cahiez，[14] Fürstner，[15]和中村[16]的团队才扩展了铁催化过程的范围，特别是通过开发芳香族格氏试剂和烷基卤化物之间的有效交叉偶联反应。[17]据我们所知，虽然已经报道了使用铁催化剂[Fe-（acac）3]，[14 c]的溴代乙烯衍生物和烷基格氏试剂之间的偶联反应，但从未报道过铁催化的卤代烷和烯基格氏试剂之间的交叉偶联反应。在此，我们报道了FeCl 3以良好至优异的产率有效地催化各种烷基卤化物和烯基格氏试剂之间的交叉偶联反应（方案1）。
Transition-metal-catalyzed CÀC bond coupling between vinyl metal reagents and unactivated alkyl halides is a useful reaction [1–3] that can be realized using copper,[4] palladium, nickel, or cobalt complexes as catalysts.[1–3, 5] For example, primary alkyl bromides can be coupled with alkenyl tin reagents using a palladium-catalyzed Stille coupling.[6] Negishi cross-coupling reactions of alkyl halides with alkenyl zinc reagents [7] or with alkenyl zirconium species [8] also proceeded in the presence of palladium complexes. Recently,[Co (acac) 3](acac= acetylacetonate) was used as a catalyst for the cross-coupling reaction of primary and secondary alkyl halides with 1-(trimethylsilyl) ethenylmagnesium.[9] This reaction was shown to proceed through a radical pathway, and the cross-coupling products were obtained in good to excellent yields. Nevertheless, 20 to 40 mol% of the cobalt complex were required, and no reaction occurred with other alkenyl Grignard reagents.[9]As synthetic organic methods are increasingly concerned with the growing importance of sustainable chemistry, ironcatalyzed cross-coupling reactions are one of the promising research areas for the construction of CÀC bonds, since iron is inexpensive and more environmentally friendly than palladium, cobalt, or nickel.[10, 11] After the pioneering works of Kochi and co-workers in the 1970s,[12, 13] only recently have the groups of Cahiez,[14] Fürstner,[15] and Nakamura,[16] extended the scope of iron-catalyzed processes, notably by developing efficient cross-coupling reactions between aromatic Grignard reagents and alkyl halides.[17] Although coupling reactions between vinyl bromide derivatives and alkyl Grignard reagents have been reported using the iron catalyst [Fe-(acac) 3],[14c] to our knowledge, the iron-catalyzed crosscoupling reaction between alkyl halides and alkenyl Grignard reagents has never been reported. Herein, we report that FeCl3 efficiently catalyzes cross-coupling reactions between various alkyl halides and alkenyl Grignard reagents in good to excellent yields (Scheme 1).