Massad Itai, Sommer Heiko, Marek Ilan
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200009, Israel.
Angew Chem Int Ed Engl. 2020 Sep 1;59(36):15549-15553. doi: 10.1002/anie.202005058. Epub 2020 Jun 5.
An in situ generated cationic Ir-catalyst isomerizes simple allylic silyl ethers into valuable, fully substituted aldehyde-derived silyl enol ethers. Importantly, by judicious choice of substrate, either of the two possible stereoisomers of a given enolate derivative is accessible with complete stereoselectivity. One-pot isomerization-aldol and isomerization-allylation processes illustrate the synthetic utility of this method.
原位生成的阳离子铱催化剂可将简单的烯丙基硅醚异构化为有价值的、完全取代的醛衍生硅基烯醇醚。重要的是，通过明智地选择底物，可以以完全的立体选择性获得给定烯醇盐衍生物的两种可能立体异构体中的任何一种。一锅异构化-羟醛反应和异构化-烯丙基化反应展示了该方法的合成效用。
