Carbonylative, Catalytic Deoxygenation of 2,3-Disubstituted Epoxides with Inversion of Stereochemistry: An Alternative Alkene Isomerization Method
作者:Jessica R. Lamb、Aran K. Hubbell、Samantha N. MacMillan、Geoffrey W. Coates
DOI:10.1021/jacs.0c02653
日期:2020.4.29
activated substrates to achieve appreciable conversion without side product formation. Motivated by stereoinvertive epoxide carbonylation reactions, we developed a two-step epoxidation/deoxygenation process that results in overall inversion of alkene stereochemistry. Unlike most deoxygenation systems, carbon monoxide was used as the terminal reductant, preventing difficult postreaction separations, given
促进烯烃立体化学反转的反应是现代有机合成领域罕见的、广受欢迎的转化。尽管存在许多异构化反应,但大多数方法需要特定的、高度活化的底物来实现可观的转化,而不会形成副产物。在立体转化环氧化物羰基化反应的推动下,我们开发了一个两步环氧化/脱氧过程,导致烯烃立体化学的整体转化。与大多数脱氧系统不同,考虑到生成的二氧化碳副产物的气态性质,一氧化碳被用作终端还原剂,防止了困难的反应后分离。各种烷基取代的顺式和反式环氧化物可以分别还原为反式和顺式烯烃,立体定向性 > 99:1,产率高达 95%,