Divergent Access to α-Carbonyl-α'-vinyl Sulfoxonium Ylides and Polysubstituted Furans from β-Ketosulfoxonium Ylides and Ynone-Esters.

Here, we describe the synthesis of novel α-carbonyl-α'-vinyl sulfoxonium ylides under ambient, catalyst-free, and additive-free conditions, demonstrating broad substrate scope and scalability using β-ketosulfoxonium ylides and α-ynone-esters. Furthermore, these ylides serve as versatile intermediates for the synthesis of highly substituted furans via Brønsted acid (-TsOH) catalysis at 130 °C. This approach offers key advantages, including wide substrate compatibility, divergent product formation from common precursors, gram-scale feasibility, and good to excellent yields.