Patel Kaushalendra, Wilczek Leonie, Calogero Francesco, Marek Ilan
Schulich Faculty of Chemistry and the Resnick Sustainability Center for Catalysis, Technion-Israel Institute of Technology, Haifa, 3200009, Israel.
J Am Chem Soc. 2025 Jun 11;147(23):19478-19484. doi: 10.1021/jacs.5c05680. Epub 2025 May 27.
We present a stereoretentive nucleophilic substitution of homoallylic tertiary alcohols via the formation of a nonclassical cyclopropyl carbinyl (CPC) carbocation intermediate. This strategy enables the creation of highly congested tertiary centers with preserved stereocontrol, addressing the typical challenges of carbocation instability and reactivity in S1 mechanisms. The stabilization of the CPC intermediate is crucial for achieving precise regio- and stereoselectivity, significantly enhancing the utility of S1-type mechanisms in complex molecule synthesis.
我们通过形成非经典环丙基甲基（CPC）碳正离子中间体，展示了高烯丙基叔醇的立体保持亲核取代反应。该策略能够构建具有高度拥挤叔中心且立体控制得以保留的结构，解决了碳正离子在SN1机制中不稳定和反应性的典型挑战。CPC中间体的稳定化对于实现精确的区域和立体选择性至关重要，显著提高了SN1型机制在复杂分子合成中的实用性。
