Oxalic Acid Monothioester for Palladium-Catalyzed Decarboxylative Thiocarbonylation and Hydrothiocarbonylation
Oxalic acid monothioester (OAM), an easily accessible and storable reagent, was reported herein as a thioester synthetic equivalent for palladium-catalyzed decarboxylative thiocarbonylation of organohalides and hydrothiocarbonylation of unsaturated carbon-carbon bonds at room temperature with high chemo- and regioselectivity. The reaction is applicable to the synthesis of cysteine-derived thioesters, thus allowing chemical modification of cysteine-containing peptides. Decarboxylation of OAM proceeds through oxidative addition of Pd(0) to the acyl-S bond, which accounts for the very mild reaction conditions.
Zhao, Bin,Fu, Yao,Shang, Rui
p. 9521 - 9526
(2019/11/28)
Transition-metal-catalyzed regioselective aroyl- and trifluoro- acetylthiolation of alkynes using thioesters
Intermolecular CO-retained carbothiolation of alkynes using thioesters took place to afford β-SR substituted enone derivatives; the choice of catalyst (Pd(dba)2-dppe) and the introduction of a CF3 group into the thioesters are the key to achieving the transformation. The Royal Society of Chemistry 2009.