Department of Chemistry, University of York, York, UK.
Nat Chem. 2023 Mar;15(3):319-325. doi: 10.1038/s41557-023-01136-x. Epub 2023 Feb 16.
Organolithium reagents are a vital tool in modern organic chemistry, enabling the synthesis of carbon-carbon bonds. However, due to their high reactivity, low temperatures, inert atmospheres and strictly dried solvents are usually necessary for their use. Here we report an encapsulating method for the stabilization of sensitive organolithium reagents-PhLi, n-BuLi and s-BuLi-in a low-cost hexatriacontane (CH) organogel. The use of this technology is showcased in nucleophilic addition reactions under ambient conditions, low-temperature bromine-lithium exchange, ortho-lithiation and C-H functionalization. The gel substantially enhances organolithium stability, allows simple storage, handling and delivery, and enables reproducible reagent portioning. The use of gels as easily divided delivery vehicles for hazardous organometallics has the potential to transform this area of synthetic chemistry, making these powerful reactions safer and more accessible to non-specialist researchers, and enabling the more widespread use of these common synthetic methods.
有机锂试剂是现代有机化学中不可或缺的工具，可用于合成碳-碳键。然而，由于其高反应性，在使用时通常需要低温、惰性气氛和严格干燥的溶剂。在这里，我们报告了一种将敏感的有机锂试剂-PhLi、n-BuLi 和 s-BuLi-稳定在低成本的三十六烷 (CH) 有机凝胶中的封装方法。该技术用于在环境条件下进行亲核加成反应、低温溴-锂交换、邻位锂化和 C-H 官能化。凝胶大大提高了有机锂的稳定性，允许简单的储存、处理和输送，并实现了可重复的试剂分装。凝胶作为危险有机金属的易于分割的输送载体的使用有可能改变这一合成化学领域，使这些强大的反应对非专业研究人员更安全、更容易获得，并使这些常见的合成方法得到更广泛的应用。
