Reductive C−C Coupling from α,β‐Unsaturated Nitriles by Intercepting Keteniminates
作者:Lillian V. A. Hale、N. Marianne Sikes、Nathaniel K. Szymczak
DOI:10.1002/anie.201904530
日期:2019.6.17
generate and intercept nitrile anion equivalents using hydrogen transfer catalysis. Addition of α,β‐unsaturated nitriles to a pincer‐based Ru−H complex affords structurally characterized κ‐N‐coordinated keteniminates by selective 1,4‐hydride transfer. When generated in situ under catalytic hydrogenation conditions, electrophilic addition to the keteniminate was achieved using anhydrides to provide α‐cyanoacetates
我们提出了一种原子经济策略,利用氢转移催化来催化生成和拦截腈阴离子当量。将α,β-不饱和腈加到基于钳的Ru-H络合物中,可通过选择性1,4-氢化物转移提供结构特征的κ-N配位的酮亚胺。当在催化氢化条件下原位生成时,使用酸酐以高收率提供了亲电性的酮亚胺酸加成物。这项工作代表了使用α,β-不饱和腈进行还原性C-C偶联反应的氢转移催化的新应用。