Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji–Trost Homologative Amination Reaction toward Allylic Amines

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(33), С. 18497 - 18505

Опубликована: Авг. 9, 2023

A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds

Язык: Английский

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Photoinduced Triphenylphosphine and Iodide Salt Promoted Reductive Decarboxylative Coupling

Advanced Science, Год журнала: 2024, Номер 11(12)

Опубликована: Янв. 17, 2024

Abstract The transient electron donor–acceptor (EDA) complex has been an emerging area in the photoinduced organic synthesis field, generating radicals without exogenous transition‐metal or dye‐based photoredox catalysts. catalytic platform to form suitable photoactive EDA complexes for photochemical reduction reactions remains underdeveloped. Herein, a general reductive alkylation via strategy is described. A simple yet multifunctional system, triphenylphosphine and iodide salt, promotes decarboxylative hydroalkylation, defluorinative of trifluoromethyl alkenes, access alkanes gem ‐difluoroalkenes. Moreover, hydroalkylation can be applied more kinds electron‐deficient alkenes as Giese addition reaction.

Язык: Английский

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Nickel-catalyzed regiodivergent hydrosilylation of α-(fluoroalkyl)styrenes without defluorination

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 28, 2024

The fluoroalkyl-containing organic molecules are widely used in drug discovery and material science. Herein, we report ligand regulated nickel(0)-catalyzed regiodivergent hydrosilylation of α-(fluoroalkyl)styrenes without defluorination, providing an atom- step-economical synthesis route two types fluoroalkyl substituted silanes with exclusive regioselectivity. anti-Markovnikov addition products (β-fluoroalkyl silanes) formed monodentate phosphine ligand. Noteworthy, the bidentate promote generation more challenging Markovnikov (α-fluoroalkyl tetrasubstituted saturated carbon centers. This protocol features easy available starting materials commercially nickel catalysis, a wide range substrates excellent structure divergent undergo variety transformations. Comprehensive mechanistic studies including inverse kinetic isotope effects demonstrate regioselectivity controlled by through α-CF3 intermediate. DFT calculations reveal distinctive mechanism involving open-shell singlet state, which is crucial for generating intricate tetra-substituted products. authors defluorination.

Язык: Английский

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Fe-Catalyzed Alkylazidation of α-Trifluoromethylalkenes: An Access to Quaternary Stereocenters Containing CF₃ and N₃ Groups

Organic Letters, Год журнала: 2023, Номер 25(8), С. 1336 - 1341

Опубликована: Фев. 23, 2023

A concise Fe-catalyzed alkylazidation of α-trifluoromethylalkenes via a C–C bond cleavage/radical addition/azidation cascade is described. This protocol features broad substrate scope, excellent functional group compatibility, and the ability to be performed on gram scale, thus offering practical step-economic approach synthetically useful tertiary α-trifluoromethyl azides.

Язык: Английский

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Divergent Synthesis of Organofluorinated Molecules from Titanium Mediated Deoxygenation of Free Alcohols

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(15), С. 1783 - 1790

Опубликована: Апрель 10, 2023

Comprehensive Summary Alcohols as among the most widely occurring organic compounds known, deoxygenative transformations of free alcohols partners in radical addition reactions remain formidable challenges with great opportunities to achieve new and useful transformations. Herein, we report a protocol via C—O bond cleavage C—C bond‐forming reaction trifluoromethyl alkenes assisted by titanium reagents strategy, enabling divergent synthesis for functional‐group‐rich organofluorinated high efficiencies. In this transformation, tertiary Ti‐catalysis could be converted alkanes without defluorination acidic conditions, while benzyl are employed Ti‐mediated activation supply gem ‐difluoroalkenes presence base. This is applicable broad range good functional group tolerance variety (including primary, secondary, alcohols), scalable gram level. Remarkably, utility demonstrated several derivatizations late‐stage functionalization drug molecules. The successful applications scale up molecules demonstrate its potential synthetic value discovery settings.

Язык: Английский

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Stable Mn(II) metal–organic framework for efficient visible light initiated trifluoromethylation reaction

Journal of Catalysis, Год журнала: 2024, Номер 436, С. 115589 - 115589

Опубликована: Июнь 4, 2024

Язык: Английский

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Stable bio-inspired Mn4O4 cubic molecular photo catalyst for effective visible light-driven C–H direct trifluoromethylation

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 116106 - 116106

Опубликована: Март 1, 2025

Язык: Английский

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Rhodium- and Iridium-Catalyzed (Enantioselective) Fluoroamidation of gem-Difluoroalkenes via Chelation Assistance

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6555 - 6562

Опубликована: Апрель 7, 2025

Язык: Английский

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Iron-catalysed reductive coupling for the synthesis of polyfluorinated compounds

Chemical Communications, Год журнала: 2022, Номер 58(100), С. 13915 - 13918

Опубликована: Янв. 1, 2022

Herein we reported the use of Earth-abundant iron as catalytic metal in presence Mn to induce difluorobromoacetates form carbon radicals, which reacted with trifluoromethyl olefins followed by β-F elimination generate corresponding gem-difluoroolefins. The cross-electrophile coupling displayed excellent functional group tolerance and broad substrate scope under mild reductive conditions, affording a large number polyfluorinated compounds, could be further transformed other valuable molecules.

Язык: Английский

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Highly Regioselective Synthesis of N‐β‐trifluoromethyl 2‐pyridones via anti‐Markovnikov Hydroamination of α‐(trifluoromethyl)styrenes with 2‐pyridones

Chemistry - An Asian Journal, Год журнала: 2023, Номер 18(10)

Опубликована: Апрель 8, 2023

Abstract A novel and facile method for the synthesis of N ‐β‐CF 3 ‐substituted 2‐pyridones via hydroamination α‐(trifluoromethyl)styrenes with was described. The reaction proceeded smoothly at room temperature, affording a variety ‐(β‐trifluoromethyl‐β‐arylethyl)pyridin‐2(1 H )‐ones in moderate to good yields excellent ‐regioselectivity.

Язык: Английский

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