Nickel-Catalyzed Cross-Electrophile Coupling of Alkyl Fluorides: Stereospecific Synthesis of Vinylcyclopropanes
Nickel-Catalyzed Cross-Electrophile Coupling of Alkyl Fluorides: Stereospecific Synthesis of Vinylcyclopropanes
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DOI：
10.1021/jacs.6b07567
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发表时间：
2016-10-26
影响因子：
15
通讯作者：
Jarvo, Elizabeth R.
中科院分区：
文献类型：
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作者：
Erickson, Lucas W.;Lucas, Erika L.;Jarvo, Elizabeth R.
报道了2-乙烯基-4-卤代四氢吡喃的立体定向还原亲电偶联反应合成乙烯基环丙烷。镍催化的反应与烷基氟化物和烷基氯化物都发生。据我们所知，这是第一次报道的交叉亲电偶联反应的烷基氟。环收缩以高立体特异性进行，提供二-和三取代的环丙烷的任一非对映体的选择性合成。该方法的实用性通过几种合成应用得到证明，包括天然产物dictyopterene A的合成。2-乙烯基-4-氟四氢呋喃也经历立体特异性环收缩，提供合成有用的羟甲基环丙烷的途径。
The stereospecific reductive cross-electrophile coupling reaction of 2-vinyl-4-halotetrahydropyrans for vinylcyclopropane synthesis is reported. The nickel-catalyzed reaction occurs with both alkyl fluorides and alkyl chlorides. To the best of our knowledge, this is the first reported cross-electrophile coupling reaction of an alkyl fluoride. Ring contraction proceeds with high stereospecificity, providing selective synthesis of either diastereomer of di- and trisubstituted cyclopropanes. The utility of this methodology is demonstrated by several synthetic applications including the synthesis of the natural product dictyopterene A. 2-Vinyl-4-fluorotetrahydrofurans also undergo stereospecific ring contractions, providing access to synthetically useful hydroxymethyl cyclopropanes.