Pd(II)-Catalyzed Enantioselective C(sp³)–H Arylation toward P-Stereogenic Dialkylphosphinamides

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 7213 - 7219

Опубликована: Апрель 24, 2024

Transition-metal-catalyzed enantioselective C–H functionalization has emerged as a promising method for the synthesis of P-stereogenic phosphorus compounds. However, previous reports are limited to C(sp2)–H bonds aryl phosphine derivatives. Herein, Pd(II)-catalyzed arylation more challenging C(sp3)–H toward dialkylphosphinamides is achieved through desymmetrization gem-diethyl groups. Various obtained with high enantioselectivities using 3,3′-CN2-H8-BINOL chiral ligand. The synthetic potential this methodology highlighted by gram-scale preparation and further derivatizations.

Язык: Английский

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Enantio-divergent C–H borylation with two different ligands from a single chiral source

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 23, 2024

Язык: Английский

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Synthesis of Chiral Saturated Heterocycles Bearing Quaternary Centers via Enantioselective β-C(sp³)–H Activation of Lactams

Journal of the American Chemical Society, Год журнала: 2024, Номер 147(2), С. 1427 - 1433

Опубликована: Дек. 31, 2024

The development of catalytic methods for the synthesis enantiopure saturated heterocycles has been a long-standing challenge in asymmetric catalysis. We describe first highly enantioselective palladium-catalyzed β-C(sp3)-H arylation and olefination lactams preparation various chiral N-heterocycles bearing quaternary carbon centers. presence strongly electron-withdrawing groups on bifunctional MPAThio ligand is crucial to reactivity weakly coordinating lactams. resulting enantioenriched are readily converted family piperidines imides that desirable drug discovery.

Язык: Английский

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Bis-CF₃-bipyridine Ligands for the Iridium-Catalyzed Borylation of N-Methylamides

ACS Catalysis, Год журнала: 2025, Номер 15(9), С. 7112 - 7120

Опубликована: Апрель 16, 2025

Bipyridine and phenanthroline are well-established neutral ligands for promoting iridium-catalyzed borylations of aromatic C-H bonds. However, their use with aliphatic substrates is almost uncharted. Herein we demonstrate that introducing CF substituents at the 5- 5'-positions bipyridine generates enable an efficient regioselective borylation methyl group in a broad variety methylamides. The reaction shows functional tolerance exhibits remarkable selectivity, offering powerful approach challenging Mechanistic investigations, including computational analysis, suggest accelerating effect ligand likely associated formation non-covalent dispersion interactions between carbonyl amide trifluoromethylated pyridine rings ligand.

Язык: Английский

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Recent synthetic methodology advancements towards all-carbon quaternary center formation and applications

Tetrahedron, Год журнала: 2025, Номер 183, С. 134711 - 134711

Опубликована: Май 14, 2025

Язык: Английский

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Enantioselective β-C(sp³)–H Nucleophilic Tosylation of Native Amides: A Synthetic Platform for Chiral Methyl Stereocenters

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

Опубликована: Май 31, 2025

Enantioselective oxygenation of unactivated C(sp3)-H bonds via asymmetric metalation remains an unsolved challenge. Herein we report the development a Pd-catalyzed, enantioselective tosylation native amides with NaOTs as nucleophile, representing rare example C-H functionalization nucleophilic coupling partner. High enantioselectivity in this reaction is achieved by chiral monoprotected amino sulfonamide (MPASA) ligands. Substantial enhancement silver salt additives was also observed. Through desymmetrization readily available isopropyl moiety, structurally diverse β-tosylated bearing α-methyl stereocenter were obtained high yield and enantioselectivity, which complements current enzymatic method for making Roche ester synthon. The tosylated products are highly versatile building blocks further diversifications nitrogen, oxygen, other nucleophiles, thus providing platform constructing methyl stereocenters.

Язык: Английский

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Pd(II)-Catalyzed Desymmetrizing gem-Dimethyl C(sp³)–H Alkenylation/Aza-Wacker Cyclization Directed by PIP Auxiliary

Organic Letters, Год журнала: 2024, Номер 26(21), С. 4457 - 4462

Опубликована: Май 22, 2024

Desymmetrization of

Язык: Английский

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Catalytic Enantioselective (3+2) Annulations of Nucleophilic Thioacyl Rh(I)-Carbenes with Achmatowicz Rearrangement Products

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8949 - 8957

Опубликована: Май 28, 2024

The cycloaddition and annulation reactions of Achmatowicz rearrangement products (ARPs) are critically important to the construction molecular complexity total synthesis natural products. However, this field is still blemished by shortage enantioselective (3+2) ARPs. Herein, we report highly enantio-, diastereo-, regioselective annulations ARPs with nucleophilic α-thioacyl Rh(I)-carbenes under Rh(I)/(R)-BINAP catalysis, producing bicyclic dihydrothiophenes multiple functionalities, three continuous chiral centers, five prochiral centers in up 97% yields 99:1 er. Mechanistically, migratory insertion following anticoordination suggested determine enantio- regioselectivities accounts for character Rh(I)-carbenes. DFT calculations revealed that enantioinduction originates from steric discrimination (R)- (S)-ARPs ligand.

Язык: Английский

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Metal-free C–H borylation of heterocycles by merging photoredox and hydrogen atom transfer catalysis

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 4785 - 4793

Опубликована: Янв. 1, 2024

Reported herein is a method that merges organophotoredox and hydrogen atom transfer catalysis to enable the C–H borylation of heterocycles using O 2 as an environmentally friendly oxidant.

Язык: Английский

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Substrate-directed C(sp³)–H borylation via transition metal catalysis: expanding the toolbox for C–H functionalization

Catalysis Science & Technology, Год журнала: 2024, Номер 14(19), С. 5488 - 5504

Опубликована: Янв. 1, 2024

Organoborons play a crucial role in organic synthesis, easing the construction of C–C and C–X bonds, which turn sensitize C(sp 3 )–H borylation reactions.

Язык: Английский

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