930573-95-8

Upstream product

• 205259-72-9 rhodium(III) tetrakis(4-tolyl)porphyrin chloride 
• 106-43-4 para-chlorotoluene 
• 591-50-4 iodobenzene 
• 624-31-7 4-tolyl iodide 
• 625-95-6 3-Iodotoluene 
• 106-38-7 para-bromotoluene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 108-88-3 toluene 

Relevant academic research and scientific papers

Aryl carbon-chlorine (Ar-Cl) and aryl carbon-fluorine (Ar-F) bond cleavages by rhodium porphyrins

Aryl carbon-chlorine (Ar-Cl) bond cleavage has been achieved with rhodium(III) tetrakis-4-tolylporphyrin chloride (Rh(ttp)Cl) to give Rh(ttp)Ar. For 4-chlorofluorobenzene, the aryl carbon-fluorine (Ar-F) bond cleavage competes with the Ar-Cl bond cleavage. Mechanistic investigations show that the Ar-Cl bond cleavage goes through metalloradical ipso-substitution mechanism, while the Ar-F bond cleavage goes through nucleophilic aromatic substitution. The selectivity of the Ar-F or Ar-Cl bond cleavage can be controlled by tuning the temperature and substrate concentration.

Base-promoted selective activation of benzylic carbon-hydrogen bonds of toluenes with rhodium(III) porphyrin chloride: Synthetic scopes and mechanism

Toluenes underwent base-promoted selective benzylic carbon-hydrogen bond activation (CHA) with rhodium porphyrin chlorides (Rh(por)Cl). In the absence of nucleophilic base, both aryl and benzylic rhodium porphyrins were formed. In the presence of nucleophilic base, the selectivity, rates and functional group compatibilities of benzylic activation reactions were enhanced. K 2CO3 was found to be the optimal base to achieve the best yields. Ortho-, meta- and para-substituted toluenes in the presence of K 2CO3 yielded the corresponding rhodium porphyrin benzyls in high yields both in solvent-free conditions and in benzene solvent. Mechanistically, in the absence of nucleophilic base, a cationic rhodium(III) porphyrin species together with some rhodium(II) porphyrin are the most likely intermediates to account both the aryl and benzylic CHA. In the presence of a base, Rh(por)OH is generated by ligand substitution with Rh(por)Cl and rapidly undergoes reduction to give rhodium(II) porphyin dimer and H2O 2. The key rhodium porphyrin intermediates for benzylic CHA were found to be rhodium(II) porphyrin dimer and hydrides as observed by 1H NMR spectroscopy, which underwent parallel benzylic CHA reactions with the rhodium(II) porphyrin dimer being the more reactive intermediate.

Base-promoted aryl carbon-iodine and carbon-bromine bond cleavage with rhodium porphyrin complexes: Scope and mechanism

Base-promoted aryl carbon-iodine and carbon-bromine bond (Ar-X, X = I, Br) cleavage by rhodium porphyrin complexes was achieved to give the rhodium(III) porphyrin aryls Rh(ttp)Ar (ttp = tetra-p-tolylporphyrinato dianion). Mechanistic studies showed that RhII2(ttp)2 is the intermediate for Ar-X (X = I, Br) cleavage. The Ar-X cleavage process goes through a rhodium(II) porphyrin radical mediated ipso-substitution mechanism.