65750-37-0

Upstream product

• 19513-78-1 1-(4-methoxy-phenyl)-2-phenoxy-ethanone 
• 811-98-3 d⁽⁴⁾-methanol 
• 112445-76-8 4-methoxyphenyl 2-phenoxyacetate 
• 1122-95-8 sodium 4-methoxyphenolate 
• 150-76-5 4-methoxy-phenol 

Downstream Products

• 93-99-2 benzoic acid phenyl ester 
• 1523-19-9 4-methoxyphenyl benzoate 
• 14314-69-3 potassium 2,4-dinitrophenolate 
• 3753-58-0 (4-methoxyphenyl) benzenesulfonate 

Relevant academic research and scientific papers

Substrate and Lewis Acid Coordination Promote O-O Bond Cleavage of an Unreactive L2CuII2(O22-) Species to Form L2CuIII2(O)2 Cores with Enhanced Oxidative Reactivity

Copper-dependent metalloenzymes are widespread throughout metabolic pathways, coupling the reduction of O2 with the oxidation of organic substrates. Small-molecule synthetic analogs are useful platforms to generate L/Cu/O2 species that reproduce the structural, spectroscopic, and reactive properties of some copper-/O2-dependent enzymes. Landmark studies have shown that the conversion between dicopper(II)-peroxo species (L2CuII2(O22-) either side-on peroxo, SP, or end-on trans-peroxo, TP) and dicopper(III)-bis(μ-oxo) (L2CuIII2(O2-)2: O) can be controlled through ligand design, reaction conditions (temperature, solvent, and counteranion), or substrate coordination. We recently published (J. Am. Chem. Soc. 2012, 134, 8513, DOI: 10.1021/ja300674m) the crystal structure of an unusual SP species [(MeAN)2CuII2(O22-)]2+ (SPMeAN, MeAN: N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) that featured an elongated O-O bond but did not lead to O-O cleavage or reactivity toward external substrates. Herein, we report that SPMeAN can be activated to generate OMeAN and perform the oxidation of external substrates by two complementary strategies: (i) coordination of substituted sodium phenolates to form the substrate-bound OMeAN-RPhO- species that leads to ortho-hydroxylation in a tyrosinase-like fashion and (ii) addition of stoichiometric amounts (1 or 2 equiv) of Lewis acids (LA’s) to form an unprecedented series of O-type species (OMeAN-LA) able to oxidize C-H and O-H bonds. Spectroscopic, computational, and mechanistic studies emphasize the unique plasticity of the SPMeAN core, which combines the assembly of exogenous reagents in the primary (phenolates) and secondary (Lewis acids association to the MeAN ligand) coordination spheres with O-O cleavage. These findings are reminiscent of the strategy followed by several metalloproteins and highlight the possible implication of O-type species in copper-/dioxygen-dependent enzymes such as tyrosinase (Ty) and particulate methane monooxygenase (pMMO).

Role of hydrogen bonding in the photophysical properties of isomeric tetrapyridylporphyrins in aprotic solvent

Extensive photophysical properties of isomeric tetra-2-pyridylporphyrin (TpyP(2)), tetra-3-pyridylporphyrin (TpyP(3)), and tetra-4-pyridylporphyrin (TpyP(4)) have been studied in the presence of a series of phenols of increasing hydrogen bonding power in

Diffusive and non-diffusive photo-induced proton coupled electron transfer from hydrogen bonded phenols to meso-tetrakis-5,10,15,20-pentafluorophenyl porphyrin

Enhanced reductive fluorescence quenching of meso-tetrakis-5,10,15,20-pentafluorophenyl porphyrin (H2F20TPP) by two different phenols, 4-methoxy phenol (4-MeOPhOH) and 2,6-dimethoxy phenol (2,6-DiMeOPhOH) in the presence of various p

Mechanistic Study of a Re-Catalyzed Monoalkylation of Phenols

A mechanistic study of a rhenium catalyzed monoalkylation of phenols is described. Reaction kinetics reveals a zero-order dependence on both alkene and phenol and a half order dependence on catalyst. Isotopic labeling studies, competition experiments, kinetic isotope effects, and Hammett analysis together afford experimental data consistent with a reversible C-H activation step and an irreversible hydrometalation process. The turnover-limiting step is identified as catalyst deaggregation. NMR studies of binary mixtures of catalyst and a single substrate (alkene or phenol) as well as those of reaction mixtures identify potential intermediates and off-cycle species. Despite the numerous Re complexes formed in these mixtures, the overall reaction is both high yielding and highly selective for monoalkylation of phenols.

Highly effective C-C bond cleavage of lignin model compounds

A highly effective method is developed for the C-C bond cleavage of lignin model compounds. The inert Cα-Cβ or Cα-Cphenyl bond of oxidized lignin model compounds was successfully converted to an active ester bond through the classic organic name reaction, Baeyer-Villiger (BV) oxidation, and thus acetal esters and aryl esters were produced in high yields (up to 99%) at room temperature. Next, K2CO3 catalyzed the alcoholysis of the resulting ester products at 45 °C, affording various useful chemical platforms in excellent yields (up to 99%), such as phenols and multifunctional esters. This method uses commercially available reagents, is transition-metal free and simple, but highly effective, and involves mild reaction conditions.