CC 双键的催化异构化是必不可少的化学转化,用于提供更高价值的类似物,在化学工业中具有重要用途。尽管在该领域取得了进展,但仍然迫切需要一种通用催化解决方案,能够精确控制环状和非环状体系中的 C=C 键迁移位置,以提供二取代和三取代烯烃。在这里,我们展示了催化量的合适的地球丰富的铁基络合物、碱和硼基化合物促进有效和可控的烯烃转位。机理研究表明,这些过程可能涉及原位形成铁氢化物物种,该物种通过顺序烯烃插入/β-氢化物消除促进烯烃异构化。通过这个策略,
Metal‐Catalyzed Remote Functionalization of ω‐Ene Unsaturated Ethers: Towards Functionalized Vinyl Species
作者:Guo‐Ming Ho、Lina Judkele、Jeffrey Bruffaerts、Ilan Marek
DOI:10.1002/anie.201802434
日期:2018.7.2
The combined ruthenium‐catalyzed chain walking with the nickel‐catalyzed cross‐coupling reaction of ω‐alkenyl ethers provide a unique entry to functionalized vinyl species. This transformation illustrates the power and flexibility of remote functionalization by demonstrating the compatibility of two independent reactions involving unrelated sites.
α,α-Chlorofluoroalkyl sulfoxides undergo nucleophilic desulfinylation with a Grignard reagent to give alkylfluorocarbenoids which collapse into cis-fluoroalkenes in the presence of copper(I) iodide.
Ir-Catalyzed Distal Branch-Selective Hydroarylation of Unactivated Internal Alkenes with Benzanilides via C–H Activation along with Consecutive Isomerization
We herein report a synergistic strategy of C–Hactivation and consecutive isomerization catalyzed by an Ir catalyst to selectively obtain branched isomers as C–H alkylated products of benzanilide derivatives. A well-tuned ligand and a directing group are crucial to achieve this selectivity. The scope of this reaction is demonstrated by the use of a variety of substituents and complex molecules.