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Regio- and Stereospecific Hydrative Cloke-Wilson Rearrangement
Haoran Wang1, Sunewang R Wang1,2
1Chang-Kung Chuang Institute, School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Lu, Shanghai 200241, China and.
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, 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.
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