Regio- and Stereospecific Hydrative Cloke–Wilson Rearrangement

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, Tf₂NH-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.