616-71-7Relevant academic research and scientific papers
Integrating Metal-Catalyzed C-H and C-O Functionalization to Achieve Sterically Controlled Regioselectivity in Arene Acylation
Serratore, Nicholas A.,Anderson, Constance B.,Frost, Grant B.,Hoang, Truong-Giang,Underwood, Steven J.,Gemmel, Philipp M.,Hardy, Melissa A.,Douglas, Christopher J.
supporting information, p. 10025 - 10033 (2018/07/21)
One major goal of organometallic chemists is the direct functionalization of the bonds most recurrent in organic molecules: C-H, C-C, C-O, and C-N. An even grander challenge is C-C bond formation when both precursors are of this category. Parallel to this is the synthetic goal of achieving reaction selectivity that contrasts with conventional methods. Electrophilic aromatic substitution (EAS) via Friedel-Crafts acylation is the most renowned method for the synthesis of aryl ketones, a common structural motif of many pharmaceuticals, agrochemicals, fragrances, dyes, and other commodity chemicals. However, an EAS synthetic strategy is only effective if the desired site for acylation is in accordance with the electronic-controlled regioselectivity of the reaction. Herein we report steric-controlled regioselective arene acylation with salicylate esters via iridium catalysis to access distinctly substituted benzophenones. Experimental and computational data indicate a unique reaction mechanism that integrates C-O activation and C-H activation with a single iridium catalyst without an exogenous oxidant or base. We disclose an extensive exploration of the synthetic scope of both the arene and the ester components, culminating in the concise synthesis of the potent anticancer agent hydroxyphenstatin.
A photoredox-neutral Smiles rearrangement of 2-aryloxybenzoic acids
Gonzalez-Gomez, Jose C.,Ramirez, Nieves P.,Lana-Villarreal, Teresa,Bonete, Pedro
, p. 9680 - 9684 (2017/11/30)
We report on the use of visible light photoredox catalysis for the radical Smiles rearrangement of 2-aryloxybenzoic acids to obtain aryl salicylates. The method is free of noble metals and operationally simple and the reaction can be run under mild batch or flow conditions. Being a redox neutral process, no stoichiometric oxidants or reductants are needed.
Carboxyl radical-assisted 1,5-aryl migration through Smiles rearrangement
Hossian, Asik,Jana, Ranjan
supporting information, p. 9768 - 9779 (2016/10/31)
We report herein, a silver(i)-catalyzed Smiles rearrangement of 2-aryloxy- or 2-(arylthio)benzoic acids to provide aryl-2-hydroxybenzoate or aryl-2-mercaptobenzoate dimer, respectively, through 1,5-aryl migration from oxygen or sulfur to carboxylate oxygen. Mechanistically, the aryl ether moiety undergoes an intramolecular ipso attack by the carboxyl radical followed by a C-O or C-S bond cleavage. Aryl-2-mercaptobenzoates undergo oxidative dimerization through a thiol moiety in situ.
Structure-activity relationships in a series of 5-[(2,5- dihydroxybenzyl)amino]salicylate inhibitors of EGF-receptor-associated tyrosine kinase: Importance of additional hydrophobic aromatic interactions
Chen,Boiziau,Parker,Mailliet,Commercon,Tocque,Le Pecq,Roques,Garbay
, p. 845 - 859 (2007/10/02)
Potent inhibitors of EGF-dependent protein tyrosine kinase (PTK) activity were synthesized in a series of 5-[(2,5-dihydroxybenzyl)amino]salicylates. Several of these compounds inhibited EGF-dependent DNA synthesis in ER 22 cells with IC50 1 μ
Synthesis of phenyl-3- and phenyl-5-acetamidosalicylates as potential analgesics
Razzak
, p. 893 - 896,894,895 (2007/10/13)
Phenylsalicylate was nitrated to obtain two nitro isomers, which were separated and reduced to the corresponding amines followed by acetylation to give phenyl-5- or phenyl-3-acetamidosalicylate. Phenyl-5-acetamidosalicylate displayed analgesic activity comparable to that of aspirin and phenacetin at doses of 25-50 mg/kg sc and was much less toxic than the latter compounds. Phenyl-3-acetamidosalicylate, however, was ineffective at a similar dose range and caused restlessness at larger doses.
