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Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions.
Nature Chemistry ( IF 19.2 ) Pub Date : 2020-02-10 , DOI: 10.1038/s41557-019-0409-4 Noam I Saper 1 , Akito Ohgi 2 , David W Small 1 , Kazuhiko Semba 2 , Yoshiaki Nakao 2 , John F Hartwig 1
Nature Chemistry ( IF 19.2 ) Pub Date : 2020-02-10 , DOI: 10.1038/s41557-019-0409-4 Noam I Saper 1 , Akito Ohgi 2 , David W Small 1 , Kazuhiko Semba 2 , Yoshiaki Nakao 2 , John F Hartwig 1
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Anti-Markovnikov additions to alkenes have been a longstanding goal of catalysis, and anti-Markovnikov addition of arenes to alkenes would produce alkylarenes that are distinct from those formed by acid-catalysed processes. Existing hydroarylations are either directed or occur with low reactivity and low regioselectivity for the n-alkylarene. Herein, we report the first undirected hydroarylation of unactivated alkenes with unactivated arenes that occurs with high regioselectivity for the anti-Markovnikov product. The reaction occurs with a nickel catalyst ligated by a highly sterically hindered N-heterocyclic carbene. Catalytically relevant arene- and alkene-bound nickel complexes have been characterized, and the rate-limiting step was shown to be reductive elimination to form the C-C bond. Density functional theory calculations, combined with second-generation absolutely localized molecular orbital energy decomposition analysis, suggest that the difference in activity between catalysts containing large and small carbenes results more from stabilizing intramolecular non-covalent interactions in the secondary coordination sphere than from steric hindrance.
中文翻译：
非共价相互作用促进未活化烯烃与未活化芳烃的镍催化反马尔可夫尼科夫加氢芳基化。
烯烃的反马尔可夫尼科夫加成一直是催化的长期目标，并且芳烃向烯烃的反马尔可夫尼科夫加成将产生与酸催化过程形成的烷基芳烃不同的烷基芳烃。现有的加氢芳基化要么是直接的，要么是在正烷基芳烃的低反应性和低区域选择性的情况下发生的。在此，我们报告了未活化烯烃与未活化芳烃的首次非定向加氢芳基化，该反应对抗马尔可夫尼科夫产物具有高区域选择性。该反应使用通过高度位阻的 N-杂环卡宾连接的镍催化剂发生。催化相关的芳烃和烯烃结合的镍配合物已被表征，并且限速步骤被证明是还原消除以形成CC键。密度泛函理论计算结合第二代绝对定域分子轨道能量分解分析表明，含有大卡宾和小卡宾的催化剂之间的活性差异更多地是由于二级配位层中分子内非共价相互作用的稳定造成的，而不是空间位阻造成的。
更新日期：2020-02-10
中文翻译：
非共价相互作用促进未活化烯烃与未活化芳烃的镍催化反马尔可夫尼科夫加氢芳基化。
烯烃的反马尔可夫尼科夫加成一直是催化的长期目标，并且芳烃向烯烃的反马尔可夫尼科夫加成将产生与酸催化过程形成的烷基芳烃不同的烷基芳烃。现有的加氢芳基化要么是直接的，要么是在正烷基芳烃的低反应性和低区域选择性的情况下发生的。在此，我们报告了未活化烯烃与未活化芳烃的首次非定向加氢芳基化，该反应对抗马尔可夫尼科夫产物具有高区域选择性。该反应使用通过高度位阻的 N-杂环卡宾连接的镍催化剂发生。催化相关的芳烃和烯烃结合的镍配合物已被表征，并且限速步骤被证明是还原消除以形成CC键。密度泛函理论计算结合第二代绝对定域分子轨道能量分解分析表明，含有大卡宾和小卡宾的催化剂之间的活性差异更多地是由于二级配位层中分子内非共价相互作用的稳定造成的，而不是空间位阻造成的。
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