C-H Functionalization-Prediction of Selectivity in Iridium(I)-Catalyzed Hydrogen Isotope Exchange Competition Reactions.
Mégane ValeroThomas KruissinkJennifer BlassRemo WeckStefan GüssregenAlleyn T PlowrightVolker DerdauPublished in: Angewandte Chemie (International ed. in English) (2020)
An assessment of the C-H activation catalyst [(COD)Ir(IMes)(PPh3 )]PF6 (COD=1,5-cyclooctadiene, IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear order of the directing groups in the hydrogen isotope exchange (HIE) with an iridium (I) catalyst. Through DFT calculations the iridium-substrate coordination complex has been identified to be the main trigger for reactivity and selectivity in the competition situation with two or more directing groups. We postulate that the competition concept found in this HIE reaction can be used to explain regioselectivities in other transition-metal-catalyzed functionalization reactions of complex drug-type molecules as long as a C-H activation mechanism is involved.
Keyphrases
- room temperature
- ionic liquid
- transition metal
- visible light
- density functional theory
- highly efficient
- reduced graphene oxide
- metal organic framework
- gas chromatography
- structural basis
- carbon dioxide
- single cell
- molecular dynamics simulations
- gold nanoparticles
- emergency department
- molecular docking
- high resolution
- drug induced
- amino acid