Regio- and Stereospecific Hydrative Cloke–Wilson Rearrangement
Haoran Wang, Sunewang R. Wang
Abstract
The Cloke–Wilson rearrangement of unsymmetrical β-diketone-derived cyclopropanes inevitably yields a mixture of two 4-acylated 2,3-dihydrofuran regiomers. By using alkynes as masked acyls, Tf 2 NH-promoted Cloke–Wilson rearrangement of polysubstituted 1-(1-alkynyl)cyclopropyl ketones followed by alkyne hydration is described, regioselectively affording 2,3-dihydrofurans bearing 4-acyls nonequivalent to that involved in the Cloke–Wilson rearrangement. The 2,3-dihydrofuran rings with cis 2,3-diaryls are unexpectedly more stable than their trans diastereomers under the reaction conditions, guaranteeing the regiospecificity of this hydrative Cloke–Wilson rearrangement with high fidelity.
Topics & Concepts
ChemistryDiastereomerStereospecificityStereochemistryCarroll rearrangementAlkyneSigmatropic reactionCatalysisOrganic chemistryCyclopropane Reaction MechanismsCatalytic Alkyne ReactionsCatalytic C–H Functionalization Methods