874299-68-0

Upstream product

• 205259-72-9 rhodium(III) tetrakis(4-tolyl)porphyrin chloride 
• 96-22-0 pentan-3-one 
• 103533-61-5 (5,10,15,20-tetrakis-4-tolylporphyrinato)(methyl)rhodium(III) 
• 936074-27-0 (5,10,15,20-tetratolylporphyrinato)(2-hydroxyethyl)rhodium(III) 
• 123-38-6 propionaldehyde 

Relevant academic research and scientific papers

Mild and selective C(CO)-C(α) bond activation of ketones with rhodium(III) porphyrin β-hydroxyethyl

Rhodium(III) porphyrin β-hydroxyethyl, RhIII(ttp)CH 2CH2OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion), was found to serve as a precursor of the highly reactive RhIII(ttp)OH for the C(CO)-C(α) bond activation (CCA) of ketones under mild and aerobic conditions of 25-50 C.

Mild and selective c(co)c(α) bond cleavage of ketones by rhodium(iii) porphyrins: Scope and mechanism

Rhodium(III) porphyrins were found to undergo selective C(CO)C(α) bond activation (CCA) of ketones promoted by water at temperatures as low as 50 °C. The acyl group of the ketone was transferred to the rhodium center, and the alkyl fragment was oxidized to a carbonyl moiety accordingly. The hydroxyl group of water is transferred to the rhodium porphyrin through hydrolysis of the kinetic α- carbonhydrogen bond activation (α-CHA) product to give RhIII(ttp)OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion), which subsequently cleaves the C(CO)C(α) bond of ketone.

Sterically enhanced, selective C(CO)-C(α) bond cleavage of a ketones by rhodium porphyrin methyl

Selective carbon(CO)-carbon(α) bond activation of ketones was achieved by rhodium(III) 5,10,15,20-tetrakis-4-toylporphyrinato methyl (Rh(ttp)Me (1)) to yield the corresponding rhodium porphyrin acyls at temperatures as low as 50 °C. More hindered isopropyl ketones were much more reactive than ethyl or methyl ketones. Rh(ttp)OH (3a) was proposed to be the intermediate to cleave the C(CO)-C(α) bond.

Activation of aldehydic carbon-hydrogen bonds under aerobic conditions by masked rhodium(III) porphyrin cation

RhIII(ttp)CH2CH2OH activated the aldehydic carbon-hydrogen bonds of functionalized aryl and enolizable aldehydes to give high yields of Rh(ttp)COR at 50 °C under both anaerobic and aerobic conditions. The Rh(ttp)(C2H4)OH intermediate was proposed to form via β-hydroxy elimination. The reactions exhibited rate and yield enhancement upon the addition of Ph3P, suggesting ligand-promoted β-elimination. The nonlinear free energy relationship of the Hammett plot suggested a multistepwise reaction with the rate-determining step (binding or activation) dependent on the electronic effect of para substituents of aryl aldehydes.