Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights
| Autor: | Rui-Xi Chen, Hai-Yang Tu, Ai-Dong Zhang, Chen-Yang Zhang, Xing Wang, Zengfeng Wei |
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| Rok vydání: | 2015 |
| Předmět: |
Reaction conditions
Nonsteroidal Tandem 010405 organic chemistry Decarboxylation Organic Chemistry Nanotechnology 010402 general chemistry 01 natural sciences Combinatorial chemistry Transformation (music) 0104 chemical sciences Benzilic acid rearrangement chemistry.chemical_compound chemistry Proton NMR Oxidative cleavage |
| Zdroj: | The Journal of organic chemistry. 81(1) |
| ISSN: | 1520-6904 |
| Popis: | The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, (1)H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, α-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials. |
| Databáze: | OpenAIRE |
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