Thioethers as Dichotomous Electrophiles for Site‐Selective Silylation via C−S Bond Cleavage
Shuai Chen, Xueying Guo, Haoran Hou, Shasha Geng, Zhengli Liu, Yun He, Xiao‐Song Xue, Feng Zhang
Abstract
The development of aryl alkyl sulfides as dichotomous electrophiles for site-selective silylation via C-S bond cleavage has been achieved. Iron-catalyzed selective cleavage of C(aryl)-S bonds can occur in the presence of β-diketimine ligands, and the cleavage of C(alkyl)-S bonds can be achieved by t-BuONa without the use of transition metals, resulting in the corresponding silylated products in moderate to excellent yields. Mechanistic studies suggest that Fe-Si species may undergo metathesis reactions during the cleavage of C(aryl)-S bonds, while silyl radicals are involved during the cleavage of C(alkyl)-S bonds.
Topics & Concepts
ElectrophileSilylationCleavage (geology)ArylAlkylChemistryBond cleavageMetathesisMedicinal chemistryStereochemistryCatalysisOrganic chemistryMaterials scienceComposite materialPolymerFracture (geology)PolymerizationSulfur-Based Synthesis TechniquesCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods