Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts.
Tian XiaZhihong WeiBrian SpiegelbergHaijun JiaoSandra HinzeJohannes G de VriesPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2018)
[Fe(PNP)(CO)HCl] (PNP=di-(2-diisopropylphosphanyl-ethyl)amine), activated in situ with KOtBu, is a highly active catalyst for the isomerization of allylic alcohols to ketones without an external hydrogen supply. High reaction rates were obtained at 80 °C, but the catalyst is also sufficiently active at room temperature with most substrates. The reaction follows a self-hydrogen-borrowing mechanism, as verified by DFT calculations. An alternative isomerization through alkene insertion and β-hydride elimination could be excluded on the basis of a much higher barrier. In alcoholic solvents, the ketone product is further reduced to the saturated alcohol.
Keyphrases
- room temperature
- ionic liquid
- density functional theory
- visible light
- metal organic framework
- molecular dynamics
- molecular dynamics simulations
- highly efficient
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- biofilm formation
- alcohol consumption
- staphylococcus aureus
- electron transfer
- monte carlo
- cystic fibrosis
- gold nanoparticles
- pseudomonas aeruginosa
- drug induced