近日，美国麻省理工学院Wendlandt, Alison E.团队报道了邻域增强H原子萃取的醇基迁移。2026年3月10日，《自然》杂志发表了这一成果。

分子结构的细微变化可导致其功能的显著改变。然而，即使是对分子进行微小的结构修饰，也常常需要完全重新合成目标分子，这给分子设计工作增加了时间和成本。近年来，针对原子替换、立体中心翻转和官能团重排等精细分子修饰的编辑方法应运而生。这些精准工具通过微调分子结构，有望简化分子功能的优化流程。

研究组报告了一种编辑方法，能够以可预测的立体和区域选择性结果，将常见的醇官能团迁移至邻近位点。该反应在激发态十聚钨酸盐阴离子促进的可逆氢原子转移催化条件下，通过1,2-酰氧基自由基迁移步骤进行。底物与试剂之间的非共价相互作用产生的邻近效应，使得在极性失配的位点上也能高效形成自由基。在合成后期应用此工具，可实现对醇官能团的精准重排；而将其与常见的醇基引入方法相结合，则为获得具有挑战性的氧化模式提供了新的合成策略。

附：英文原文

Title: Alcohol group migration by proximity-enhanced H atom abstraction

Author: Xu, Qian, Nie, Yichen, Haaksma, Jacob-Jan, Zhang, Ronghua, Holmberg-Douglas, Natalie, van der Mei, Farid, Scola, Paul M., Williams, Chloe, Johnson, Jeremiah A., Wendlandt, Alison E.

Issue&Volume: 2026-03-10

Abstract: Subtle changes in molecular structure can lead to profound changes in molecular function. However, even minor structural refinements can require the complete re-synthesis of a target molecule, adding time and cost to molecular design campaigns1. Recently, editing methods have emerged targeting subtle molecular perturbations, including atomic substitution, stereocenter inversion and functional group repositioning2. These precision tools hold the potential to streamline the optimization of molecular function by fine-tuning molecular structure. Here we report an editing method that enables the migration of common alcohol functional groups to proximal sites with predictable stereo- and regiochemical outcomes. The reaction proceeds through a 1,2-acyloxy radical migration step under reversible H atom transfer catalysis conditions promoted by excited state decatungstate polyanion. Proximity effects arising from non-covalent interactions between substrate and reagent enable efficient radical formation at polarity-mismatched positions. Application of this tool at a late synthetic stage allows for the precise re-positioning of alcohol functional groups, while integration with common alcohol group installation methods provides new synthetic strategies to access challenging oxygenation patterns.

DOI: 10.1038/s41586-026-10347-4

Source: https://www.nature.com/articles/s41586-026-10347-4