Stridfeldt Elin, Lindstedt Erik, Reitti Marcus, Blid Jan, Norrby Per-Ola, Olofsson Berit
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91, Stockholm, Sweden.
Pharmaceutical Sciences, AstraZeneca Gothenburg, 431 83, Mölndal, Sweden.
Chemistry. 2017 Sep 21;23(53):13249-13258. doi: 10.1002/chem.201703057. Epub 2017 Sep 5.
A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.
利用实验技术和密度泛函理论（DFT）计算，对脂肪醇和氢氧化物与二芳基碘鎓盐进行芳基化反应生成烷基芳基醚和二芳基醚的机理进行了研究。已捕获了芳炔中间体，并发现了避免由芳炔产生副产物的添加剂。观察到与芳基化反应并行的醇氧化途径；这表明其通过分子内机制进行。比较了通过配体偶联和芳炔生成产物的途径，发现与醇反应时四配位过渡态更有利。此外，在与缺电子二芳基碘鎓盐的反应中确定了一种新的直接亲核取代途径。
