Hydrogenation of Alkenes via Cooperative Hydrogen Atom Transfer,Journal of the American Chemical Society

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Hydrogenation of Alkenes via Cooperative Hydrogen Atom Transfer
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-10-29 , DOI: 10.1021/jacs.0c09544
Padmanabha V. Kattamuri ₁ , Julian G. West ₁

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Radical hydrogenation via hydrogen atom transfer (HAT) to alkenes is an increasingly important transformation for the formation of thermodynamic alkane isomers. Current single-catalyst methods require stoichiometric oxidant in addition to hydride (H-) source to function. Here we report a new approach to radical hydrogenation: cooperative hydrogen atom transfer (cHAT), where each hydrogen atom donated to the alkene arrives from a different catalyst. Further, these hydrogen atom (H•) equivalents are generated from complementary hydrogen atom precursors, with each alkane requiring one hydride (H-) and one proton (H+) equivalent and no added oxidants. Preliminary mechanistic study supports this reaction manifold and shows the intersection of metal-catalyzed HAT and thiol radical trapping HAT catalytic cycles to be essential for effective catalysis. Together, this unique catalyst system allows us to reduce a variety of unactivated alkene substrates to their respective alkanes in high yields and diastereoselectivities and introduces a new approach to radical hydrogenation.

中文翻译：

通过协同氢原子转移对烯烃进行加氢

通过氢原子转移 (HAT) 向烯烃的自由基氢化是形成热力学烷烃异构体的越来越重要的转化。目前的单一催化剂方法除了需要氢化物 (H-) 源外还需要化学计量的氧化剂才能发挥作用。在这里，我们报告了一种自由基氢化的新方法：协同氢原子转移 (cHAT)，其中每个提供给烯烃的氢原子来自不同的催化剂。此外，这些氢原子 (H•) 等价物由互补的氢原子前体产生，每个烷烃需要一个氢化物 (H-) 和一个质子 (H+) 等价物，并且不添加氧化剂。初步机理研究支持这种反应歧管，并表明金属催化的 HAT 和硫醇自由基捕获 HAT 催化循环的交叉点对于有效催化至关重要。

更新日期：2020-10-29

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