Hydroalkylation of Unactivated Olefins via Visible-Light-Driven Dual Hydrogen Atom Transfer Catalysis,Journal of the American Chemical Society

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Hydroalkylation of Unactivated Olefins via Visible-Light-Driven Dual Hydrogen Atom Transfer Catalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-07-16 , DOI: 10.1021/jacs.1c05852
Guangyue Lei ₁ , Meichen Xu ₁ , Rui Chang ₁ , Ignacio Funes-Ardoiz ₂ , Juntao Ye ₁

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Radical hydroalkylation of olefins enabled by hydrogen atom transfer (HAT) catalysis represents a straightforward means to access C(sp³)-rich molecules from abundant feedstock chemicals without the need for prefunctionalization. While Giese-type hydroalkylation of activated olefins initiated by HAT of hydridic carbon–hydrogen bonds is well-precedented, hydroalkylation of unactivated olefins in a similar fashion remains elusive, primarily owing to a lack of general methods to overcome the inherent polarity-mismatch in this scenario. Here, we report the use of visible-light-driven dual HAT catalysis to achieve this goal, where catalytic amounts of an amine-borane and an in situ generated thiol were utilized as the hydrogen atom abstractor and donor, respectively. The reaction is completely atom-economical and exhibits a broad scope. Experimental and computational studies support the proposed mechanism and suggest that hydrogen-bonding between the amine-borane and substrates is beneficial to improving the reaction efficiency.

中文翻译：

通过可见光驱动的双氢原子转移催化未活化烯烃的加氢烷基化

通过氢原子转移 (HAT) 催化实现的烯烃自由基加氢烷基化代表了一种直接获得 C( sp ³)-丰富的分子来自丰富的原料化学品，无需预官能化。虽然由氢化碳-氢键的 HAT 引发的活性烯烃的 Giese 型加氢烷基化是有先例的，但未活化烯烃以类似方式的加氢烷基化仍然难以捉摸，主要是由于缺乏克服固有极性不匹配的通用方法。设想。在这里，我们报告了使用可见光驱动的双 HAT 催化来实现这一目标，其中催化量的胺硼烷和原位生成的硫醇分别用作氢原子提取物和供体。该反应是完全原子经济的，具有广泛的范围。

更新日期：2021-07-28

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