[1,4]-S- to O-silyl migration: multicomponent synthesis of α-thioketones through chemoselective transformation of esters to ketones with organolithium reagents.
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.
Key Laboratory of Drug Targeting and Drug Delivery Systems of the Education Ministry, Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu, 610041 (P.R. China).
Xianwei
X
Sun
Zhenlei
Z
Song
Hongze
H
Li
Changzheng
C
Sun
D004952:Esters; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D012825:Silicon / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry
D004952:Esters; D007659:Ketones; D009942:Organometallic Compounds; D013455:Sulfur; D008094:Lithium; D010100:Oxygen; D012825:Silicon
multicomponent reactions; nucleophilic addition; organolithium reagents; silyl migration; thioketones