Chen Chih-Ming, Kuo Tung-Chun, Reddy Julakanti Satyanarayana, Teoh Yi Ning, Huang Jyun-Sian, Lin Sheng-Kuo, Cheng Mu-Jeng, Hsieh Hsing-Pang
Institute of Biotechnology and Pharmaceutical Research, National Health Research Institutes, Miaoli County 350, Taiwan, ROC.
Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan, ROC.
Org Lett. 2025 Aug 8;27(31):8394-8398. doi: 10.1021/acs.orglett.5c01574. Epub 2025 Jul 25.
The influence of allylic substituent orientation on the six-membered fused ring, as well as the steric hindrance at the alkene bridge (R and R) and bridgehead (R), on the thiol-mediated acyl radical rearrangement/cyclization of bicyclo[2.2.2]octenone was investigated. A combined analysis using density functional theory calculations and interaction region indicator analysis suggests that reaction selectivity is driven by functional group noncovalent interactions.
研究了烯丙基取代基取向对六元稠环的影响,以及烯烃桥(R和R)和桥头(R)处的空间位阻对双环[2.2.2]辛烯酮的硫醇介导的酰基自由基重排/环化反应的影响。使用密度泛函理论计算和相互作用区域指示剂分析的联合分析表明,反应选择性受官能团非共价相互作用驱动。