Organosodium compounds for catalytic cross-coupling
Organosodium compounds for catalytic cross-coupling
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DOI：
10.1038/s41929-019-0250-6
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发表时间：
2019-04-01
期刊：
影响因子：
37.8
通讯作者：
Takai, Kazuhiko
中科院分区：
文献类型：
--
作者：
Asako, Sobi;Nakajima, Hirotaka;Takai, Kazuhiko
钠是地壳和海洋中最丰富的碱金属。然而，有机钠化合物一直被认为不如有机锂化合物，而有机锂化合物在上个世纪主导了合成有机化学。尽管由于其反应性质而在很大程度上被忽视，但鉴于对可持续合成的需求日益增长，而无需求助于锂等不太丰富的元素，因此值得重新探索有机钠化学。在本文中，我们证明，与普遍的看法相反，有机钠化合物可以很容易地从芳基氯或（杂）芳烃和易于处理的钠分散体制备，并且在被transmetallated到相应的锌和硼化合物后，它们很容易参与根岸和铃木-宫浦交叉偶联反应，有机合成中的基本碳-碳键形成反应。与有机钠物质的直接偶联反应也是可能的。
Sodium is the most abundant alkali metal in the Earth's crust and the ocean. However, organosodium compounds have long been considered inferior to organolithium compounds, which have instead dominated synthetic organic chemistry during the last century. Despite being largely neglected because of their reactive nature, it is worth re-exploring organosodium chemistry, in light of the growing demand for sustainable syntheses without recourse to less abundant elements such as lithium. Herein, we demonstrate that, contrary to common belief, organosodium compounds can be easily prepared from aryl chlorides or (hetero) arenes and easy-to-handle sodium dispersion and, after being transmetallated to the corresponding zinc and boron compounds, they readily participate in the Negishi and Suzuki-Miyaura cross-coupling reactions, fundamental carbon-carbon bond-forming reactions in organic synthesis. Direct coupling reactions with organosodium species were also possible.