Organic Letters, Год журнала: 2023, Номер 25(3), С. 565 - 568
Опубликована: Янв. 13, 2023
Acyl fluorides are versatile reagents in organic synthesis. However, there is no precedent to employ acyl as radical precursors. We herein report an N-heterocyclic nitrenium iodide salt-catalyzed photoreduction of produce radicals, which could react with 2-isocyanobiaryls afford various carbonyl phenanthridines.
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2325 - 2332
Опубликована: Янв. 17, 2024
The only known method for the dearomative trifluoromethoxylation of indoles is preliminary, with one substrate successfully undergoing reaction. In this study, we not developed a broadly applicable indole but also achieved divergent by fine-tuning reaction conditions. Under optimized conditions, silver salt and an easily handled OCF3 reagent, various smoothly underwent dearomatization to afford diverse array ditrifluoromethoxylated indolines in 50–84% isolated yields up 37:1 diastereoselectivity, fluorinated trifluoromethoxylated were obtained exclusive trans selectivity. addition, conditions compatible other heteroaromatic rings as well styrene moieties.
Язык: Английский
Процитировано
12
Nature Communications, Год журнала: 2024, Номер 15(1)
Опубликована: Май 21, 2024
Abstract Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by inherent preference an inner-sphere mechanism. Here, we present a demonstration outer-sphere mechanism in Rh-catalyzed reaction simple using gem -difluorinated cyclopropanes as allyl surrogates. This unconventional offers opportunity fluorine recycling via C − F bond cleavage/reformation, ultimately delivering carbofluorination products. The developed method tolerates wide range alkenes, providing access to secondary, tertiary fluorides and -difluorides with 100% atom economy. DFT calculations reveal that formation goes through unusual nucleophilic allyl-Rh species instead migration insertion, generated carbon cation then forms tetrafluoroborate fluoride shuttle.
Язык: Английский
Процитировано
12
ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3181 - 3190
Опубликована: Фев. 14, 2024
Cross-coupling reactions have been well received as one of the most popular protocols for ketone synthesis. As an important coupling partner, bench-stable and commercially available alkyl boronic acids are widely used in transition metal catalysis, but they rarely utilized radical precursors acylative reactions. Herein, we reported energy-transfer-enabled acylation using free via NHC/photo dual catalysis. This protocol could efficiently promote Suzuki-type cross-coupling between acyl imidazoles multicomponent alkylacylations alkenes, thus producing various ketones with structural diversity. Additionally, products can readily transform into a large number structurally interesting fine chemicals. Preliminary mechanistic studies shed light on unique reaction mechanism.
Язык: Английский
Процитировано
11
Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(4), С. 1056 - 1085
Опубликована: Янв. 1, 2023
In this tutorial, reaction scopes, limitations and mechanisms of radical acylations are summarized discussed according to types catalytic systems.
Язык: Английский
Процитировано
24
Organic Letters, Год журнала: 2023, Номер 25(3), С. 565 - 568
Опубликована: Янв. 13, 2023
Acyl fluorides are versatile reagents in organic synthesis. However, there is no precedent to employ acyl as radical precursors. We herein report an N-heterocyclic nitrenium iodide salt-catalyzed photoreduction of produce radicals, which could react with 2-isocyanobiaryls afford various carbonyl phenanthridines.
Язык: Английский
Процитировано
23