Silver-Catalyzed Vinylcarbene Insertion into C–C Bonds of 1,3-Diketones with Vinyl-<i>N</i>-triftosylhydrazones
Yong Wu, Yongquan Ning, Xin‐Yue Han, Peiqiu Liao, Ying Xia, Paramasivam Sivaguru, Xihe Bi
Abstract
We describe the silver-catalyzed formal insertion of a vinylcarbene into unstrained C(CO)–C bonds of 1,3-diketones using vinyl-N-triftosylhydrazones as vinylcarbene precursors. This method allows the rapid synthesis of otherwise inaccessible 2-vinyl-substituted 1,4-diketones from relatively simple substrates. This mild catalytic protocol exhibits a good functional group tolerance and substrate scope and allows for good chemoselectivity control. The preliminary theoretical calculations suggest that the reaction proceeds through a stepwise enol cyclopropanation/retro-aldol pathway.
Topics & Concepts
ChemistryChemoselectivityCatalysisUmpolungEnolSubstrate (aquarium)Functional groupCyclopropanationMedicinal chemistryStereochemistryPolymer chemistryOrganic chemistryPolymerGeologyNucleophileOceanographyCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsCatalytic Alkyne Reactions