Stereoselective Access to Fully Substituted Aldehyde-Derived Silyl Enol Ethers by Iridium-Catalyzed Alkene Isomerization
Itai Massad
Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa, 3200009 Israel
Search for more papers by this authorDr. Heiko Sommer
Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa, 3200009 Israel
Search for more papers by this authorCorresponding Author
Prof. Dr. Ilan Marek
Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa, 3200009 Israel
Search for more papers by this authorItai Massad
Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa, 3200009 Israel
Search for more papers by this authorDr. Heiko Sommer
Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa, 3200009 Israel
Search for more papers by this authorCorresponding Author
Prof. Dr. Ilan Marek
Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Technion City, Haifa, 3200009 Israel
Search for more papers by this authorDedicated to Professor Moris Eisen on the occasion of his 60th birthday
Graphical Abstract
Zig-zag forever: An Ir-based alkene isomerization catalyst generates fully substituted aldehyde enolate derivatives with complete stereocontrol, starting from simple silylated allylic alcohols. The stereo- and regioselectivity of isomerization are dictated by the preference towards zig-zig-shaped allyliridium hydride intermediates, enabling selective access to either stereoisomer of a given enolate.
Abstract
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.
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