A selenium-catalysed para-amination of phenols

作者：Yan, Dingyuan; Wang, Guoqiang; Xiong, Feng; Sun, Wei-Yin; Shi, Zhuangzhi; Lu, Yi^*; Li, Shuhua^*; Zhao, Jing^*

来源：Nature Communications, 2018, 9(1): 4293.

DOI：10.1038/s41467-018-06763-4

• CHALCOGEN-CHALCOGEN INTERACTIONS
• LEWIS-BASE CATALYSIS
• GLUTATHIONE-PEROXIDASE
• ORGANOSELENIUM COMPOUNDS
• THIOREDOXIN REDUCTASE
• EXPEDIENT SYNTHESIS
• SELENOCYSTEINE
• ALKENES
• FUNCTIONALIZATION
• PURIFICATION

Antioxidant enzyme glutathione peroxidase (GPx) decomposes hydroperoxides by utilizing the different redox chemistry of the selenium and sulfur. Here, we report a Se-catalysed para-amination of phenols while, in contrast, the reactions with sulfur donors are stoichiometric. A catalytic amount of phenylselenyl bromide smoothly converts N-aryloxyacetamides to N-acetyl p-aminophenols. When the para position was substituted (for example, with tyrosine), the dearomatization 4,4-disubstituted cyclodienone products were obtained. A combination of experimental and computational studies was conducted and suggested the weaker Se-N bond plays a key role in the completion of the catalytic cycle. Our method extends the selenium-catalysed processes to the functionalisation of aromatic compounds. Finally, we demonstrated the mild nature of the para-amination reaction by generating an AlEgen 2-(2'-hydroxyphenyl)benzothiazole (HBT) product in a fluorogenic fashion in a PBS buffer.

• 出版日期2018-10-16
• 单位南京大学