Metal-catalyzed Thiomethylation of Chloroarenes and Diverse Aryl Electrophiles DOI Creative Commons

Satoshi Toyoda,

Keiichiro Iizumi,

Junichiro Yamaguchi

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this study, we report the first development of metal catalyzed methylthiolation chloroarenes and diverse aromatic electrophiles, addressing persistent challenges catalyst intermediate deactivation in functionalization less reactive substrates. To overcome these issues, designed a novel anion-shuttle-type agent, 4-((methylthio)methyl)morpholine, which enables controlled situ release methylthiolate anions, thereby preventing poisoning enhancing reactivity. This strategy allows efficient not only but also broad range aryl including bromoarenes, triflates, tosylates, pivalates, nitriles, carboxylic acids. The developed system exhibits excellent functional group compatibility, making it applicable to derivatization pharmaceuticals natural products. Furthermore, detailed mechanistic investigations revealed key factors underlying exceptional efficiency providing new insights into C-S bond formation under practical conditions.

Language: Английский

One-Pot Stepwise Dechalcogenization of Trisulfides to Unsymmetrical Dialkyl Thioethers DOI

Jiuwen Xu,

Ying Chen, Weidong Rao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

The construction of C-S bonds has garnered significant interest due to the ubiquitous presence organosulfur compounds in natural products and bioactive molecules. Herein, we report a one-pot, stepwise desulfuration strategy employing trisulfides as precursors for synthesis unsymmetrical dialkylthioethers. Our study demonstrates that copper powder facilitates conversion into disulfides, which subsequently undergo nickel-catalyzed reductive coupling afford desired products. This approach provides practical, odorless, broadly applicable method

Language: Английский

Citations

0
Metal-catalyzed Thiomethylation of Chloroarenes and Diverse Aryl Electrophiles DOI Creative Commons

Satoshi Toyoda,

Keiichiro Iizumi,

Junichiro Yamaguchi

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this study, we report the first development of metal catalyzed methylthiolation chloroarenes and diverse aromatic electrophiles, addressing persistent challenges catalyst intermediate deactivation in functionalization less reactive substrates. To overcome these issues, designed a novel anion-shuttle-type agent, 4-((methylthio)methyl)morpholine, which enables controlled situ release methylthiolate anions, thereby preventing poisoning enhancing reactivity. This strategy allows efficient not only but also broad range aryl including bromoarenes, triflates, tosylates, pivalates, nitriles, carboxylic acids. The developed system exhibits excellent functional group compatibility, making it applicable to derivatization pharmaceuticals natural products. Furthermore, detailed mechanistic investigations revealed key factors underlying exceptional efficiency providing new insights into C-S bond formation under practical conditions.

Language: Английский

Citations

0