Transition-Metal-Free C2-Functionalization of Pyridines through Aryne Three-Component Coupling |
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Authors: | Avishek Guin Subrata Bhattacharjee Prof Dr Akkattu T Biju |
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Institution: | Department of Organic Chemistry, Indian Institute of Science, Bangalore, 560012 India |
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Abstract: | The direct C2-functionalization of pyridines through a transition-metal-free protocol by using aryne multicomponent coupling is demonstrated. The reaction allowed a broad-scope synthesis of C2-substituted pyridine derivatives bearing the −CF3 group in good yields with α,α,α-trifluoroacetophenones as the third component. Activated keto esters could also be employed as the third component in this formal 1,2-di(hetero)arylation of ketones. Performing the reaction under dilute conditions inhibited the competing pyridine–aryne polymerization pathway. Nucleophilic attack by the initially generated pyridylidene intermediate on the carbonyl followed by an SNAr process resembling the Smiles rearrangement affords the desired products. |
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Keywords: | arynes multicomponent coupling pyridine Smiles rearrangement transition-metal-free reactions |
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