Ruthenium catalyzed β-selective alkylation of vinylpyridines with aldehydes/ketones via N2H4 mediated deoxygenative couplings

Umpolung (polarity reversal) tactics of aldehydes/ketones have greatly broadened carbonyl chemistry by enabling transformations with electrophilic reagents and deoxygenative functionalizations. Herein, we report the first ruthenium-catalyzed beta-selective alkylation of vinylpyridines with both naturally abundant aromatic and aliphatic aldehyde/ketones via N2H4 mediated deoxygenative couplings. Compared with one-electron umpolung of carbonyls to alcohols, this two-electron umpolung strategy realized reductive deoxygenation targets, which were not only applicable to the regioselective alkylation of a broad range of 2/4-alkene substituted pyridines, but also amenable to challenging 3-vinyl and steric-embedded internal pyridines as well as their analogous heterocyclic structures.

Automated summary

This study reports the first ruthenium-catalyzed beta-selective alkylation of vinylpyridines with both aromatic and aliphatic aldehyde/ketones via N2H4 mediated deoxygenative couplings. The two-electron umpolung strategy realized reductive deoxygenation targets, allowing for regioselective alkylation of a broad range of substituted pyridines.