Qi Liang-Wen, Twumasi Emmanuella Bema, Li Xiao-Wei, Li Rui, Lu Yixin
Department of Chemistry, National University of Singapore 3 Science Drive 3 117543 Singapore
Chem Sci. 2024 Dec 13;16(3):1441-1446. doi: 10.1039/d4sc06273f. eCollection 2025 Jan 15.
The [5,5]-sigmatropic rearrangement is a less-studied reaction and may be strategically utilized to devise unique synthetic processes. Herein, we document a diboron-enabled [5,5]-sigmatropic rearrangement for practical synthesis of BINAM derivatives. Mechanistically, a concerted activation of azonaphthalenes by diboron creates a unique ten-membered transition state, which subsequently triggers a [5,5]-sigmatropic rearrangement. The reaction occurs under mild conditions, and offers operational simplicity, remarkable chemo- and regioselectivities, and good scalability (>10 grams).
[5,5] - 迁移重排是一种研究较少的反应，可从策略上加以利用以设计独特的合成方法。在此，我们报道了一种用于实际合成联萘胺衍生物的二硼促进的[5,5] - 迁移重排反应。从机理上讲，二硼对联萘并萘的协同活化产生了一个独特的十元过渡态，随后引发[5,5] - 迁移重排。该反应在温和条件下进行，操作简便，具有出色的化学和区域选择性，且具有良好的可扩展性（> 10克）。
