Stereospecific Synthesis of E-Alkenes through Anti-Markovnikov Hydroalkylation of Terminal Alkynes
Stereospecific Synthesis of E-Alkenes through Anti-Markovnikov Hydroalkylation of Terminal Alkynes
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DOI：
10.1021/jacs.9b04800
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发表时间：
2019-08-14
影响因子：
15
通讯作者：
Lalic, Gojko
中科院分区：
文献类型：
--
作者：
Hazra, Avijit;Chen, Jason;Lalic, Gojko
我们发展了一种由端炔和碘代烷立体定向合成E-烯烃的方法。加氢烷基化反应通过铜和镍催化剂的协同作用实现，并且以优异的反马尔可夫尼科夫选择性进行。我们证明了反应的广泛范围，这可以在酯，腈，芳基溴，醚，烷基氯，苯胺，和广泛的含氮杂芳族化合物的存在下完成。机理研究提供的证据表明，铜催化剂活化的炔加氢铜化，控制区域和非对映选择性的整体反应。镍催化剂活化烷基碘并促进与烯基铜中间体的交叉偶联。
We have developed a method for stereospecific synthesis of E-alkenes from terminal alkynes and alkyl iodides. The hydroalkylation reaction is enabled by a cooperative action of copper and nickel catalysts and proceeds with excellent anti-Markovnikov selectivity. We demonstrate the broad scope of the reaction, which can be accomplished in the presence of esters, nitriles, aryl bromides, ethers, alkyl chlorides, anilines, and a wide range of nitrogen-containing heteroaromatic compounds. Mechanistic studies provide evidence that the copper catalyst activates the alkyne by hydrocupration, which controls both the regio- and diastereoselectivity of the overall reaction. The nickel catalyst activates the alkyl iodide and promotes cross coupling with the alkenyl copper intermediate.