Sercel Zachary P, Marek Ilan
Schulich Faculty of Chemistry and the Resnick Sustainability Center for catalysis. Technion -, Israel Institute of Technology Technion City, Haifa, 3200009, Israel.
Angew Chem Int Ed Engl. 2025 Mar 3;64(10):e202421235. doi: 10.1002/anie.202421235. Epub 2025 Feb 10.
Disclosed herein is the reaction of silyllithium reagents with quaternary-substituted arylbicyclobutanes to diastereoselectively form polysubstituted cyclobutylsilanes by C-C bond cleavage. The bicyclobutanes are generated in situ, by lithium-halogen exchange, from readily accessible (bromomethyl)iodocyclopropane precursors, rendering this a one-pot transformation. The trapping of a generated cyclobutyllithium intermediate with an electrophile was also demonstrated, providing a cyclobutane product with vicinal quaternary stereocenters. The utility of the cyclobutylsilane products was showcased by Tamao-Fleming oxidation to prepare a quaternary-substituted cyclobutanol.
本文公开了甲硅烷基锂试剂与季碳取代的芳基双环丁烷反应，通过碳-碳键裂解非对映选择性地形成多取代环丁基硅烷。双环丁烷通过锂-卤交换，由易于获得的（溴甲基）碘环丙烷前体原位生成，从而实现一锅法转化。还证明了用亲电试剂捕获生成的环丁基锂中间体，得到具有邻位季碳立体中心的环丁烷产物。通过玉尾-弗莱明氧化反应制备季碳取代的环丁醇，展示了环丁基硅烷产物的实用性。
