1,4 -S- to O-silyl migration: Multicomponent synthesis of α-thioketones through chemoselective transformation of esters to ketones with organolithium reagents

Article abstract of DOI:10.1002/chem.201303459

A [1,4]-S- to O-silyl migration has been exploited to chemoselectively transform esters into ketones by using organolithium reagents, allowing multicomponent synthesis of α-thioketones. Mechanistic studies reveal that this migration proceeds in an intramolecular manner and is more favorable than the corresponding [1,5]-S- to O- and [1,3]-C- to O-silyl migrations. The resulting α-thioketones are valuable building blocks for the synthesis of cyclic or multifunctionalized organosulfur compounds. Productive move: A [1,4]-S- to O-silyl migration has been exploited to chemoselectively transform esters into ketones by using organolithium reagents, allowing the multicomponent synthesis of α-thioketones (see scheme, TMEDA = tetramethylethylenediamine). Mechanistic studies revealed that this migration proceeds in an intramolecular manner and is more favorable than the corresponding [1,5]-S- to O- and [1,3]-C- to O-silyl migrations. The resulting α-thioketones are valuable building blocks for the synthesis of cyclic or multifunctionalized organosulfur compounds.