Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters

Abstract

Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources. † Electronic supplementary information (ESI) available. See

Recent developments in palladium-catalyzed C–S bond formation

“…As a seminal work, Wu and co-workers developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides (88) with thioethers and thioesters (89) to afford a broad range of the corresponding thiomethylation and carbonylative thiomethylation products (>70 examples) in good to excellent yields with satisfying functional group compatibility (Scheme 34). 58 Moreover, this method provided the first example of carbonylative methylthioesterification of aryl halides under the similar reaction conditions. The scope of this system showed that both electron-poor and -rich substrates could be converted into the desired products with alkyl sulfides as the sulfur source.…”

Supported Palladium‐Gold Catalyzed Carbonylative Methylthioesterification of Aryl Iodides using Oxalic acid and DMSO as CO and CH3SH Surrogates

“…reported the synthesis of methylthio‐esters from thioethers and thioesters following trans‐thioetherification of aryl halides under homogeneous palladium chloride, Xantphos ligand at 20 bar CO gas pressure (Scheme 1). [10] …”

Chemoselective N-acylation of indoles using thioesters as acyl source

“…In 2019, Jiang and co-workers reported a dicarbonylation of amine and aryl borates using α-ketothioester as a stable 1,2-dicarbonyl reagent [ 16 ] ( Scheme 1 , B). Recently, we applied S -methyl butanethioate in a Pd-catalyzed transthioetherification or transthioesterification of aryl halides for the synthesis of thioethers and thioesters [ 17 ] ( Scheme 1 , C). In addition, we also used this reagent to trap alkylcopper(I) intermediates and to form C−S bonds [ 18 ].…”