Search

This article discusses the synthesis of alkyl aryl ethers using diaryliodonium salts. Alkyl aryl ethers are commonly found in pharmaceuticals, agrochemicals, and functional materials. The authors propose a new method using main-group mediators to overcome the limitations of current synthetic strategies. They conducted experiments to identify the scope and limitations of the reaction and discuss the mechanistic implications of their findings, including the potential formation of arynes and the oxidation of alcohols. The article also explores the development of a method for O-arylation of aliphatic alcohols using aryl(TMP)iodonium salts, which is compatible with various types of alcohols and aryl groups. The authors conducted experiments to understand the mechanisms involved and ruled out certain background reactions. They observed the formation of aryne intermediates in some reactions but concluded that arynes are unlikely to mediate the oxidation of benzyl alcohol under the given conditions. [Extracted from the article]

Herein, we describe a synthetic approach for arylation that exploits the in situ formation and reaction of an unsymmetrical diaryliodonium salt. In this way, aryl iodides are used as reagents in a metal‐free reaction with phenols, and a trimethoxyphenyl (TMP) group is used as a "dummy" group to facilitate transfer of a wide range of aryl moieties. The scope of aryl electrophiles and phenol nucleophiles is broad (>30 examples) and the yields are high (52–95%, 80% avg.). One‐pot coupling reactions avoid the synthesis of diaryliodonium salts and provide opportunities for sequential reactions and novel chemoselectivity. [ABSTRACT FROM AUTHOR]

The Endochin-Like Quinolone (ELQ) compound class may yield effective, safe treatments for a range of important human and animal afflictions. However, to access the public health potential of this compound series, a synthetic route needed to be devised that lowers costs and is amenable to large scale production. In the new synthetic route described here, a substituted β-keto ester, formed by an Ullmann reaction and subsequent acylation, is reacted with an aniline via a Conrad-Limpach reaction to produce 3-substituted 4(1H)-quinolones such as ELQ-300 and ELQ-316 . This synthetic route, the first described to be truly amenable to industrial scale production, is relatively short (5 reaction steps), does not require palladium, chromatographic separation or protecting group chemistry, and may be performed without high vacuum distillation.