The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 Israel.
Nat Chem. 2016 Mar;8(3):209-19. doi: 10.1038/nchem.2445.
Exploiting the reactivity of one functional group within a molecule to generate a reaction at a different position is an ongoing challenge in organic synthesis. Effective remote functionalization protocols have the potential to provide access to almost any derivatives but are difficult to achieve. The difficulty is more pronounced for acyclic systems where flexible alkyl chains are present between the initiating functional group and the desired reactive centres. In this Review, we discuss the concept of remote functionalization of alkenes using metal complexes, leading to a selective reaction at a position distal to the initial double bond. We aim to show the vast opportunity provided by this growing field through selected and representative examples. Our aim is to demonstrate that using a double bond as a chemical handle, metal-assisted long-distance activation could be used as a powerful synthetic strategy.
在有机合成中,利用分子中一个官能团的反应性在不同位置引发反应是一个持续的挑战。有效的远程官能团化方法有可能获得几乎任何衍生物,但很难实现。对于存在于起始官能团和所需反应中心之间的无环系统,这种困难更为明显,因为在这些系统中存在灵活的烷基链。在这篇综述中,我们讨论了使用金属配合物对烯烃进行远程官能团化的概念,导致在初始双键远端的位置发生选择性反应。我们旨在通过选择和有代表性的例子展示这个不断发展的领域所提供的巨大机会。我们的目的是证明,使用双键作为化学处理手段,金属辅助的远程活化可以作为一种强大的合成策略。