One of the main goals for modern synthesis is to develop distinct reaction pathways from identical starting materials for the efficient synthesis of diverse compounds. Herein, we disclose the unique...
The selective installation of functional groups at the pyridylic position is of significant interest in synthetic and medicinal chemistry. In their Research Article (e202204217), Sungwoo Hong et al. report the successful C−H functionalization of the heterobenzylic site of pyridines and quinolines by orchestrating cascade reactions on a modular photochemical platform. This reaction offers a powerful synthetic tool for the rational modification of heterobenzylic C−H bonds in complex settings under mild conditions.
An efficient pyridylic C(sp 3 )À H functionalization has been developed through photocatalytic radicalmediated fluoroalkylation or cascade reactions. This method is enabled by the reversible formation of alkylidene dihydropyridine intermediates via the facile enolate formation of C4-alkyl N-amidopyridinium salts in the absence of an external base, thereby establishing the conditions necessary for subsequent intermolecular radical trapping. Rapid structural diversification of the pyridylic site can be achieved through photocatalytic multicomponent cascade reactions involving alkene trifluoromethylation, SO 2 -reincorporation, and sulfonyl radical addition. This operationally simple method features a broad substrate scope and high chemoselectivity and offers a unique approach for the rational modification of the heterobenzylic CÀ H bonds of pyridines and quinolines with uniform site-selective control. Furthermore, experimental and theoretical studies were performed to elucidate the reaction mechanism.
An efficient pyridylic C(sp3)−H functionalization has been developed through photocatalytic radical‐mediated fluoroalkylation or cascade reactions. This method is enabled by the reversible formation of alkylidene dihydropyridine intermediates via the facile enolate formation of C4‐alkyl N‐amidopyridinium salts in the absence of an external base, thereby establishing the conditions necessary for subsequent intermolecular radical trapping. Rapid structural diversification of the pyridylic site can be achieved through photocatalytic multicomponent cascade reactions involving alkene trifluoromethylation, SO2‐reincorporation, and sulfonyl radical addition. This operationally simple method features a broad substrate scope and high chemoselectivity and offers a unique approach for the rational modification of the heterobenzylic C−H bonds of pyridines and quinolines with uniform site‐selective control. Furthermore, experimental and theoretical studies were performed to elucidate the reaction mechanism.
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