Jiang Yiyuan, Yorimitsu Hideki
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
JACS Au. 2022 Oct 31;2(11):2514-2521. doi: 10.1021/jacsau.2c00375. eCollection 2022 Nov 28.
The reduction of styrenes with lithium arenide in a flow microreactor leads to the instantaneous generation of highly unstable radical anions that subsequently dimerize to yield the corresponding 1,4-organodilithiums. A flow reactor with fast mixing is essential for this reductive dimerization as the efficiency and selectivity are low under batch conditions. A series of styrenes undergo dimerization, and the resulting 1,4-organodilithiums are trapped with various electrophiles. Trapping with divalent electrophiles affords precursors for useful yet less accessible cyclic structures, for example, siloles from dichlorosilanes. Thus, we highlight the power of single-electron reduction of unsaturated compounds in flow microreactors for organic synthesis.
在流动微反应器中用芳基锂还原苯乙烯会导致瞬间生成高度不稳定的自由基阴离子，这些自由基阴离子随后二聚生成相应的1,4 - 有机二锂化合物。对于这种还原二聚反应，具有快速混合功能的流动反应器至关重要，因为在间歇条件下效率和选择性较低。一系列苯乙烯发生二聚反应，生成的1,4 - 有机二锂化合物会与各种亲电试剂反应。用二价亲电试剂捕获可得到有用但较难获得的环状结构的前体，例如由二氯硅烷得到硅杂环戊二烯。因此，我们强调了在流动微反应器中对不饱和化合物进行单电子还原用于有机合成的强大功能。
