Manganese-Catalyzed Synthesis of Quaternary Peroxides: Application in Catalytic Deperoxidation and Rearrangement Reactions
| Autor: | Moreshwar B. Chaudhari, Moseen A Shaikh, Akash S Ubale, Boopathy Gnanaprakasam |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Steric effects Ketone 010405 organic chemistry Chemistry Organic Chemistry chemistry.chemical_element Manganese 010402 general chemistry 01 natural sciences Aldehyde Combinatorial chemistry Reversible reaction 0104 chemical sciences Catalysis Bipyridine chemistry.chemical_compound Bond cleavage |
| Zdroj: | The Journal of organic chemistry. 85(16) |
| ISSN: | 1520-6904 |
| Popis: | Highly efficient, selective, and direct C-H peroxidation of 9-substituted fluorenes has been achieved using a Mn-2,2'-bipyridine catalyst via radical-radical cross-coupling. Moreover, this method effectively promotes the vicinal bisperoxidation of sterically hindered various substituted arylidene-9H-fluorene/arylideneindolin-2-one derivatives to afford highly substituted bisperoxides with high selectivity over the oxidative cleavage of C═C bond that usually forms the ketone of an aldehyde. Furthermore, a new approach for the synthesis of (Z)-6-benzylidene-6H-benzo[c]chromene has been achieved via an acid-catalyzed skeletal rearrangement of these peroxides. For the first time, unlike O-O bond cleavage, reductive C-O bond cleavage in peroxides using the Pd catalyst and H2 is described, which enables the reversible reaction to afford exclusively deperoxidized products. A detailed mechanism for peroxidation, molecular rearrangement, and deperoxidation has been proposed with preliminary experimental evidences. |
| Databáze: | OpenAIRE |
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