Mechanisms and Origins of Regioselectivity in Rare-Earth-Catalyzed C–H Functionalization of Anisoles and Thioanisoles

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

The direct catalytic C–H functionalization of aromatic compounds such as anisoles and thioanisoles is great interest significance. However, achieving precise regioselectivity remains a major challenge. In this study, we conducted comprehensive density functional theory calculations to explore the mechanisms rare-earth-catalyzed regioselective alkylation, borylation, silylation anisole thioanisole. results reveal that in cationic alkylation systems, alkene insertion step follows substrate-assisted mechanism, which an additional substrate molecule acts ligand facilitate transformation. neutral borylation although mononuclear hydride species readily dimerize into binuclear due thermodynamic stability, process predominantly proceeds via pathway. Furthermore, origins were thoroughly elucidated. A detailed analysis electronic steric effects related transition states reveals that, for anisole, primarily governed by ring strain. Since α-C(sp3)–H activation involves formation highly strained three-membered ring, reaction preferentially occurs at ortho-C(sp2)–H site, forming less four-membered ring. contrast, thioanisole, play decisive role, driving more negatively charged α-C(sp3) site stronger metal–carbon interactions.

Language: Английский

Unconventional reactivity of sulfonyl fluorides

Trends in Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

N-Fluorosulfurylamidines Enable Modular Synthesis of 1,5-Disubstituted Tetrazoles

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9395 - 9400

Published: Oct. 24, 2024

Here we report the modular synthesis of 1,5-disubstituted tetrazoles using two highly chemoselective reactions, ligations N-fluorosulfurylamidines with amines and diazotransfer reactions between FSO2N3 N-monosubstituted amidines, respectively. Enabled by sulfur(VI) fluoride exchange (SuFEx) click chemistry, have successfully synthesized a series identified them as stable scalable organic synthons. We then discover that react selectively toward aliphatic amines, resulting in formation amidines can further to deliver tetrazoles. Our work provides new platform for generating library diverse structures, which is unprecedented.

Language: Английский