Sodium is the most abundant alkali metal on Earth. Despite being an attractive choice for sustainable synthesis, organosodium compounds are rarely used in organic synthesis and have been overshadowed to date by organolithium compounds. This situation is largely due to the lack of convenient and efficient methods for the preparation of organosodium compounds. We report herein a halogen–sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds, many of them previously inaccessible by other methods. The key discovery is the use of a bulky alkylsodium lacking a β-hydrogen, readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion, which retards undesired reactions such as Wurtz–Fittig coupling and β-hydrogen elimination, and enables efficient halogen-sodium exchange. We believe that the efficiency, generality, and convenience of the present method will open new horizons for the use of organosodium in organic synthesis, ultimately contributing to the development of sustainable chemistry by replacing the currently dominant organolithium reagents.

钠是地球上最丰富的碱金属。尽管有机钠化合物是可持续合成的诱人选择，但有机合成中很少使用有机钠化合物，迄今为止，有机钠化合物已经掩盖了有机钠化合物。这种情况主要是由于缺乏方便有效的制备有机钠化合物的方法。我们在这里报告了一种卤素-钠交换方法，以制备各种（杂）芳基和烯基钠化合物，其中许多以前是其他方法无法获得的。关键发现是使用缺少β-氢的大体积烷基钠，该烷基钠易于从新戊酰氯和易于处理的钠分散液就地制备，从而延缓了Wurtz–Fittig偶联和β等不良反应-氢消除，并实现有效的卤素-钠交换。我们相信，本方法的效率，通用性和便利性将为有机钠在有机合成中的使用开辟新的视野，最终通过取代目前占主导地位的有机锂试剂为可持续化学的发展做出贡献。