Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids
Eric Palomo, Akhilesh K. Sharma, Zhaofeng Wang, Liyin Jiang, Feliu Maseras, Marcos G. Suero
Abstract
We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class of transient donor/acceptor Rh(II)-carbenes evolved through a cyclopropanation process providing access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations allowed the analysis of the properties of Rh(II)-carbynoids and acyloxy Rh(II)-carbenes as well as the characterization of the mechanism.
Topics & Concepts
ChemistryCyclopropanationRhodiumCatalysisAcceptorMedicinal chemistryCarbeneStereochemistryOrganic chemistryCondensed matter physicsPhysicsCyclopropane Reaction MechanismsCatalytic Alkyne ReactionsSynthetic Organic Chemistry Methods