52482-62-9Relevant articles and documents
Late-Stage C-H Alkylation of Heterocycles and 1,4-Quinones via Oxidative Homolysis of 1,4-Dihydropyridines
Gutiérrez-Bonet, álvaro,Remeur, Camille,Matsui, Jennifer K.,Molander, Gary A.
supporting information, p. 12251 - 12258 (2017/09/12)
Under oxidative conditions, 1,4-dihydropyridines (DHPs) undergo a homolytic cleavage, forming exclusively a Csp3-centered radical that can engage in the C-H alkylation of heterocyclic bases and 1,4-quinones. DHPs are readily prepared from aldehydes, and considering that aldehydes normally require harsh reaction conditions to take part in such transformations, with mixtures of alkylated and acylated products often being obtained, this net decarbonylative alkylation approach becomes particularly useful. The present method takes place under mild reaction conditions and requires only persulfate as a stoichiometric oxidant, making the procedure suitable for the late-stage C-H alkylation of complex molecules. Notably, structurally complex pharmaceutical agents could be functionalized or prepared with this protocol, such as the antimalarial Atovaquone and antitheilerial Parvaquone, thus evidencing its applicability. Mechanistic studies revealed a likely radical chain process via the formation of a dearomatized intermediate, providing a deeper understanding of the factors governing the reactivity of these radical forebears.
Photochemical Reactions of Caffeine with Aliphatic Aldehydes
Erndt, Aleksander,Fiedorowicz, Maciej,Kostuch, Andrzej,Para, Andrzej
, p. 1043 - 1046 (2007/10/02)
Photochemical reactions of caffeine with several aliphatic aldehydes are performed.In the reactions with ethanal, propanal and butanal stable 8-acyl-8,9-dihydrocaffeines 2 and 3 together with unreduced 8-acylcaffeines 4 and 8-(α-hydroxy-alkyl)caffeines 6 are produced.Under similar conditions, the reactions of 2-methylpropanal, 2-methylbutanal and 2,2-dimethylbutanal resulted in the formation of the corresponding 8-alkylcaffeines 7. - Key Words: Caffeine / Aldehydes / Photochemistry / Purines