664987-32-0Relevant articles and documents
Mechanistically Driven Development of an Iron Catalyst for Selective Syn-Dihydroxylation of Alkenes with Aqueous Hydrogen Peroxide
Borrell, Margarida,Costas, Miquel
supporting information, p. 12821 - 12829 (2017/09/25)
Product release is the rate-determining step in the arene syn-dihydroxylation reaction taking place at Rieske oxygenase enzymes and is regarded as a difficult problem to be resolved in the design of iron catalysts for olefin syn-dihydroxylation with potential utility in organic synthesis. Toward this end, in this work a novel catalyst bearing a sterically encumbered tetradentate ligand based in the tpa (tpa = tris(2-methylpyridyl)amine) scaffold, [FeII(CF3SO3)2(5-tips3tpa)], 1 has been designed. The steric demand of the ligand was envisioned as a key element to support a high catalytic activity by isolating the metal center, preventing bimolecular decomposition paths and facilitating product release. In synergistic combination with a Lewis acid that helps sequestering the product, 1 provides good to excellent yields of diol products (up to 97% isolated yield), in short reaction times under mild experimental conditions using a slight excess (1.5 equiv) of aqueous hydrogen peroxide, from the oxidation of a broad range of olefins. Predictable site selective syn-dihydroxylation of diolefins is shown. The encumbered nature of the ligand also provides a unique tool that has been used in combination with isotopic analysis to define the nature of the active species and the mechanism of activation of H2O2. Furthermore, 1 is shown to be a competent synthetic tool for preparing O-labeled diols using water as oxygen source.
Synthesis of Stereoisomeric Medium-Ring α,α′-Dihydroxy Cycloalkanones
Paquette, Leo A.,Hartung, Ryan E.,Hofferberth, John E.,Vilotijevic, Ivan,Yang, Jiong
, p. 2454 - 2460 (2007/10/03)
The stereochemical course of the epoxidation of the silyl enol ethers of 2-tert-butyldimethylsilyl-oxycycloheptanone and -cyclooctanone has been investigated and shown to proceed exclusively anti to the existing α-substituent. 2-(Benzyloxy)cyclooctanone b
