Site-Selective α-Alkoxylation of Iodonium Ylides with Alcohols via Ruthenium Catalysis.

Herein, we report an efficient ruthenium-catalyzed α-alkoxylation of structurally diverse iodonium ylides with a wide range of primary, secondary, and tertiary alcohols under mild conditions. This strategy provides a versatile platform for the synthesis of diverse 3-alkoxylated 4-hydroxycoumarins and related analogues. The reaction exhibits high site-selectivity, a wide substrate scope, good functional group tolerance, and scale-up synthesis. Additionally, this work not only expands the application scope of hypervalent iodine reagents but also offers a practical and safer alternative to diazo compounds for C-O bond formation while broadening substrate scope.