Applied Catalysis A General, Год журнала: 2024, Номер unknown, С. 120084 - 120084
Опубликована: Дек. 1, 2024
Язык: Английский
Organic Letters, Год журнала: 2024, Номер unknown
Опубликована: Окт. 30, 2024
Bis(trifluoromethyl)carbinols are valuable pharmacophores, yet their synthesis is challenging, largely due to a scarcity of safe and effective bis(trifluoromethyl)carbinolation reagents. Here, we realized the hydrobis(trifluoromethyl)carbinolation alkenes, utilizing stable readily accessible 2,2-bis(trifluoromethyl)glycolic acid as source both bis(trifluoromethyl)carbinol unit hydrogen atom. This process leverages photoinduced Fe-LMCT-enabled radical decarboxylation that generates key intermediate. Our mild protocol facilitates diverse range alkyl bis(trifluoromethyl)carbinols, including structurally complex molecules with pharmaceutical relevance.
Язык: Английский
Процитировано
2
Chinese Journal of Chemistry, Год журнала: 2024, Номер unknown
Опубликована: Дек. 2, 2024
Comprehensive Summary Herein, we report a rare example of three‐component net‐oxidative sulfonylation SO 2 surrogate with an oxidatively activated radical precursor under mild and metal‐ external‐oxidant‐free conditions. The mildness sustainability the reaction are enabled by photoelectrocatalysis, 3‐aza‐1,5‐dienes, organotrifluoroborates 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO) undergo sulfonylative cyclization to afford sulfono 4‐pyrrolin‐2‐ones in atom‐economical manner broad substrate scope good functional‐group tolerance. protocol is amenable late‐stage diversification complex molecular architectures as well gram‐scale synthesis. Sunlight could be used light source, conducted all‐solar mode using commercially available photovoltaic panel generate electricity situ . Mechanistic studies reveal that generated (DABCO), which was generally innocent previous reactions, functions electron shuttle between photocatalytic cycle reactants.
Язык: Английский
Процитировано
2
Опубликована: Июнь 25, 2024
The selection of electrode material is a critical factor that determines the selectivity electrochemical organic reactions. However, fundamental principles governing this relationship are still largely unexplored. Herein, we demonstrate photoelectrocatalytic (PEC) system as promising reaction platform for selective radical–radical coupling owing to inherent charge-transfer properties photoelectrocatalysis. As model reaction, radical trifluoromethylation arenes shown on hematite photoanodes without employing molecular catalysts. PEC exhibited superior mono- bis-trifluoromethylated product compared conventional methods utilizing conducting anodes. Electrochemical and density functional theory (DFT) computational studies revealed controlling kinetics anodic oxidation aromatic substrates essential increasing selectivity. Only configuration could generate sufficiently high-energy charge carriers with controlled due generation photovoltage charge-carrier recombination, which characteristic features semiconductor photoelectrodes. This study opens novel approach towards reactions through understanding intrinsic physicochemical semiconducting materials.
Язык: Английский
Процитировано
1
Chemical Science, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Semiconducting photoanodes could generate high-energy charge carriers with controlled kinetics due to generation of photovoltage and recombination. The inherent charge-transfer properties enabled the efficient selective radical–radical coupling.
Язык: Английский
Процитировано
1
Applied Catalysis A General, Год журнала: 2024, Номер unknown, С. 120084 - 120084
Опубликована: Дек. 1, 2024
Язык: Английский
Процитировано
1