With sodium being the most abundant alkali metal on Earth, organosodium compounds are an attractive choice for sustainable chemical synthesis. However, organosodium compounds are rarely used—and are overshadowed by organolithium compounds—because of a lack of convenient and efficient preparation methods. Here we report a halogen–sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds including tri- and tetrasodioarenes, many of them previously inaccessible by other methods. The key discovery is the use of a primary and bulky alkylsodium lacking β-hydrogens, which retards undesired reactions, such as Wurtz–Fittig coupling and β-hydrogen elimination, and enables efficient halogen–sodium exchange. The alkylsodium is readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion. We believe that the efficiency, generality, and convenience of the present method will contribute to the widespread use of organosodium in organic synthesis, ultimately contributing to the development of sustainable organic synthesis by rivalling the currently dominant organolithium reagents.

由于钠是地球上最丰富的碱金属，有机钠化合物是可持续化学合成的有吸引力的选择。然而，由于缺乏方便有效的制备方法，有机钠化合物很少被使用，并被有机锂化合物所掩盖。在这里，我们报告了一种卤素-钠交换方法，用于制备多种（杂）芳基和烯基钠化合物，包括三和四钠芳烃，其中许多以前无法通过其他方法获得。关键发现是使用缺乏 β-氢的伯级和大体积烷基钠，它可以延缓不需要的反应，例如 Wurtz-Fittig 偶联和 β-氢消除，并实现有效的卤素-钠交换。烷基钠很容易从新戊基氯和易于处理的钠分散液中原位制备。