The dynamic translocation of a metal catalyst along an alkyl side chain — often coined as ‘chain-walking’ — has opened new retrosynthetic possibilities that enable functionalization at unactivated C(sp³)–H sites. The use of nickel complexes in chain-walking strategies has recently gained considerable momentum owing to their versatility for forging sp³ architectures and their redox promiscuity that facilitates both one-electron or two-electron reaction manifolds. This Review discusses the relevance and impact that these processes might have in synthetic endeavours, including mechanistic considerations when appropriate. Particular emphasis is given to the latest discoveries that leverage the potential of Ni-catalysed chain-walking scenarios for tackling transformations that would otherwise be difficult to accomplish, including the merger of chain-walking with other new approaches such as photoredox catalysis or electrochemical activation.

金属催化剂沿烷基侧链的动态易位（通常称为“链游”）开辟了新的逆合成可能性，使未活化的 C（sp³）-H 位点官能化成为可能。镍配合物在链式行走策略中的使用最近获得了相当大的动力，因为它们在锻造 sp³ 结构方面的多功能性以及有助于单电子或双电子反应歧管的氧化还原混杂性。本综述讨论了这些过程在合成工作中可能产生的相关性和影响，包括适当时的机制考虑。特别强调了利用镍催化链步走方案的潜力来解决原本难以完成的转变的最新发现，包括链步走与其他新方法（如光氧化还原催化或电化学活化）的合并。