Chen Fushan, Cao Zhu, Zhu Chen
Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Angew Chem Int Ed Engl. 2025 Mar 10;64(11):e202424667. doi: 10.1002/anie.202424667. Epub 2025 Jan 31.
Along with the renaissance of radical chemistry, the past decade has witnessed rapid development in radical-mediated rearrangement reactions. A wide diversity of radical approaches harnessing functional-group migration (FGM) have been devised to enhance both synthetic efficiency and molecular complexity. However, the application of FGM reactions to construct stereogenic centers remains underexplored owing to the inherent challenges of asymmetric radical reactions. In this Minireview, we summarize the emerging area of asymmetric functionalization involving radical-mediated FGM reactions. Enantioselectivity can be regulated by chiral substrates, auxiliaries or reagents, or achieved through asymmetric transition-metal catalysis. This synthetic strategy demonstrates its superiority in the production of valuable complex molecules that are otherwise difficult to obtain by conventional methods.
随着自由基化学的复兴，过去十年见证了自由基介导的重排反应的快速发展。人们设计了各种各样利用官能团迁移（FGM）的自由基方法，以提高合成效率和分子复杂性。然而，由于不对称自由基反应的固有挑战，FGM反应在构建立体中心方面的应用仍未得到充分探索。在这篇综述中，我们总结了涉及自由基介导的FGM反应的不对称官能团化这一新兴领域。对映选择性可以通过手性底物、助剂或试剂来调节，或者通过不对称过渡金属催化来实现。这种合成策略在生产有价值的复杂分子方面显示出其优越性，而这些分子用传统方法很难获得。
