Scalable Birch reduction with lithium and ethylenediamine in tetrahydrofuran
Scalable Birch reduction with lithium and ethylenediamine in tetrahydrofuran
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DOI：
10.1126/science.abk3099
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发表时间：
2021-11-05
期刊：
影响因子：
56.9
通讯作者：
Koide, Kazunori
中科院分区：
文献类型：
--
作者：
Burrows, James;Kamo, Shogo;Koide, Kazunori
Birch还原将芳烃脱芳构化为1，4-环己二烯。尽管大量的努力致力于避免氨和低温条件，传统的，繁琐的，危险的程序仍然是标准。在乙二胺中用锂进行的Benkeser还原将芳烃转化为环己烯和环己烷的混合物;这比Birch还原操作更容易，但不提供1，4-环己二烯。在这里，我们报告了在环境温度下，在四氢呋喃中，由锂和乙二胺（或类似物）促进的Birch还原。我们的方法易于建立，价格低廉，可扩展，快速，可用于任何化学实验室，并且能够减少富电子和缺电子底物。我们的方案也与有机铜酸盐化学相容，用于进一步官能化。
The Birch reduction dearomatizes arenes into 1,4-cyclohexadienes. Despite substantial efforts devoted to avoiding ammonia and cryogenic conditions, the traditional, cumbersome, and dangerous procedure remains the standard. The Benkeser reduction with lithium in ethylenediamine converts arenes to a mixture of cyclohexenes and cyclohexanes; this is operationally easier than the Birch reduction but does not afford 1,4-cyclohexadienes. Here, we report a Birch reduction promoted by lithium and ethylenediamine (or analogs) in tetrahydrofuran at ambient temperature. Our method is easy to set up, inexpensive, scalable, rapid, accessible to any chemical laboratory, and capable of reducing both electron-rich and electron-deficient substrates. Our protocol is also compatible with organocuprate chemistry for further functionalization.