Department of Chemistry, Emory University, Atlanta, GA 30322, USA.
Angew Chem Int Ed Engl. 2011 Sep 26;50(40):9370-3. doi: 10.1002/anie.201103568. Epub 2011 Aug 30.
The combined C—H functionalization/Cope rearrangement (CHCR) is a highly diastereoselective process that typically proceeds through a chair transition state. A recent computational study of a model system for the CHCR reaction revealed that a boat transition state was only slightly less favored than a chair transition state. Guided by these computational results, this study describes the design of substrates that would react by means of a boat transition state. The resulting C—H functionalization products are the opposite diastereomeric series to what had been previously obtained with this chemistry.
C—H 功能化/Cope 重排（CHCR）是一个高度非对映选择性的过程，通常通过椅式过渡态进行。最近对 CHCR 反应模型体系的计算研究表明，船过渡态仅略低于椅过渡态有利。受这些计算结果的启发，本研究设计了通过船过渡态进行反应的底物。得到的 C—H 功能化产物与之前用这种化学方法得到的产物是相反的非对映异构体系列。
