An Umpolung Oxa-[2,3] Sigmatropic Rearrangement Employing Arynes for the Synthesis of Functionalized Enol Ethers
Rahul N. Gaykar, Malini George, Avishek Guin, Subrata Bhattacharjee, Akkattu T. Biju
Abstract
An oxa-[2,3] sigmatropic rearrangement involving arynes is reported featuring the umpolung of ketones, where the C═O bond polarity is reversed. The in situ-generated sulfur ylides from β-keto thioethers and arynes undergo efficient rearrangement allowing the facile and robust synthesis of functionalized enol ethers in high yields and excellent functional group compatibility. Preliminary mechanistic studies rule out the possibility of Pummerer-type rearrangement operating in this case.
Topics & Concepts
UmpolungChemistrySigmatropic reactionAryneEnolCope rearrangementFunctional groupCombinatorial chemistryStereochemistryOrganic chemistryNucleophileCatalysisPolymerCyclization and Aryne ChemistryCatalytic Alkyne ReactionsAsymmetric Synthesis and Catalysis