Photocatalytic Three-Component Reductive Coupling Synthesis of gem-Difluorohomoallyl Secondary Amines

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

gem-Difluorohomoallyl amines, an important class of gem-difluoroalkenes, are prevalent moieties in many bioactive compounds. However, limited methods suitable for the synthesis this type compound containing secondary amines. Here, we display a photocatalytic multicomponent protocol gem-difluoroalkenes which makes use readily available materials: arylamines, alkyl aldehydes, and α-trifluoromethyl alkenes. Moreover, ketones amines also substrates. Preliminary mechanistic experiments indicate that key α-amino radical was involved, generated from reduction situ-formed imines (or iminium ions) by reduced photocatalyst. Subsequent addition to alkenes β-F elimination deliver desired products.

Язык: Английский

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Nickel-Catalyzed Asymmetric Homobenzylic Hydroamidation of Aryl Alkenes to Access Chiral β-Arylamides

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Herein, we introduce a Ni-catalyzed asymmetric homobenzylic hydroamidation reaction that efficiently addresses the dual challenges of achieving regio- and enantioselectivity in synthesis β-(hetero)arylethylamides. By employing transposed NiH catalysis approach, this method facilitates formation key chiral nickel-amido intermediates, enabling insertion into alkenes to produce desired β-arylamide products with excellent enantioselectivity. The exhibits high functional group tolerance utilizes readily available starting materials vinylarenes react dioxazolone as robust amidating source. Notably, approach was successfully applied pharmaceutical compounds natural products, such Clobenzorex, Direx, Selegiline, Sacubitril, Cipargamin.

Язык: Английский

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α,α-Difluorinated Allylsulfones: gem-Difluoroethylenyl Reagents for Synthesis of Fluorinated Chiral α-Quaternary Amino Acids

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Among numerous fluorine-containing molecules, chiral gem-difluoroethylenes (C═CF2) exhibited unique properties in agrochemicals, pharmaceuticals, and materials science. However, the general synthetic methods were limited to functionalization/defluorination of trifluoromethylalkenes. Here, we disclose a new type difluoroethylenyl reagent, α,α-difluoro allylsulfones, which allows highly enantioselective Cu-catalyzed desulfonylative SN2′ substitution with benzylideneamino esters. This protocol presents novel strategy for construction diversified α-quaternary amino acid derivatives containing gem-difluoroethylene moiety excellent results (up 86% yield, generally 90–98% ee). The ease synthesis applications this protocol, transformations products revealed potential utility chemistry.

Язык: Английский

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Photoredox-Catalyzed Alkylamination of Alkenes via Oxidative Radical-Polar Crossover and Site-Selective 1,5-Hydrogen Atom Transfer

Organic Letters, Год журнала: 2024, Номер 26(32), С. 6847 - 6852

Опубликована: Авг. 7, 2024

We reported the visible-light-mediated photoredox-catalyzed oxidative radical-polar crossover and 1,5-hydrogen atom transfer combined site-selective remote C(sp

Язык: Английский

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Direct C–H difluoroallylation of α,β-unsaturated amides and aryl amides by rhodium catalysis

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The first example of Rh-catalyzed C(sp 2 )–H difluoroallylation α,β-unsaturated amides with 3-bromo-3,3-difluoropropene has been developed under mild conditions.

Язык: Английский

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Photoredox Catalyzed Reductive Trifluoromethylation of Imines via radical umpolung strategy

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

A photocatalyzed radical-umpolung strategy is developed to synthesize trifluoromethylated α-unnatural amino acids and amines. This method involves the migration of an N-centred radical through aromatic framework construct C–CF 3 bond.

Язык: Английский

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Decatungstate-Photocatalyzed Transformations of 2-Bromo-3,3,3-trifluoropropene for Selective Synthesis of Z/E-β-CF₃-Enones

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 2, 2024

Condition-controlled switchable and divergent transformations of cost-effective 2-bromo-3,3,3-trifluoropropene (BTP) aldehydes were realized using a decatungstate (TBADT)-photocatalyzed strategy. The hydroacylated products, i.e., β,β-Br,CF

Язык: Английский

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Photocatalyzed cascade hydrogen atom transfer for the construction of α-CF₃-1,4-diketones

Organic Chemistry Frontiers, Год журнала: 2024, Номер unknown

Опубликована: Дек. 5, 2024

A TBADT-photocatalyzed cascade hydrogen atom transfer procedure was established for the synthesis of α-CF 3 -1,4-diketones from aldehydes and 2-bromo-3,3,3-trifluoro-1-propenes.

Язык: Английский

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