Kinetic Resolution of Racemic Radicals in Asymmetric Photoredox Minisci Reactions with Azaarenes for Precise Construction of Two Non-adjacent Stereocenters

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

Опубликована: Март 11, 2025

Despite the significant potential of photocatalysis as a robust synthetic tool, high reactivity radicals often presents challenges in achieving optimal chemoselectivity. In this study, we demonstrate that inherent limitation can be strategically harnessed for asymmetric photoredox catalysis. By utilizing chiral catalyst to facilitate kinetic resolution between two enantiomers racemic radical intermediates, one enantiomer selectively undergoes desired transformation, while noncatalytic side reactions deplete other enantiomer. Consequently, an attractive three-component Minisci-type reaction involving bromides, homoallylic tertiary alcohols or amines, and azaarenes has been developed. This approach enables efficient assembly amines onto nonadjacent β-position azaarene-functionalized carbon stereogenic center with levels enantio- diastereoselectivity. Therefore, method not only allows direct utilization readily available feedstocks are challenging convert into prochiral via redox processes but also provides strategy synthesizing complex molecules multiple stereocenters.

Язык: Английский

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Visible-Light-Driven C,N-Selective Heteroarylation of N-Fluoroalkyl Hydroxylamine Reagents with Quinoxalin-2(1H)-ones

Organic Letters, Год журнала: 2023, Номер 25(48), С. 8693 - 8699

Опубликована: Ноя. 22, 2023

Herein, we disclose a direct and powerful strategy for the synthesis of highly valuable α-trifluoromethylamine N-trifluoroethylamine derivatives from visible-light-promoted C,N-selective heteroarylation N-trifluoroethyl hydroxylamine reagents with quinoxalin-2(1H)-ones under ambient conditions. The chemoselectivity process (trifluoroalkylation or N-trifluoroethylamination) can easily be dictated modulated by selection substrates. key to success is protecting group on N atom reagents, which control 1,2-H shift in situ-generated radical. Remarkable features this method include mild conditions, easy operation, high selectivity, excellent functional tolerability. More importantly, trifluoroalkylated products readily derivatized into other interesting imidazo-fused heterocycles that would great potential exploitation pharmaceutically relevant molecules.

Язык: Английский

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Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 21, 2024

A sequential process via photoredox catalysis and Lewis acid mediation for C-F bond transformation of the CF

Язык: Английский

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Direct enantioselective reduction of C=C bond of β-polyfluoro-alkylated enones via asymmetric photoredox catalysis

Science China Chemistry, Год журнала: 2024, Номер 67(6), С. 2016 - 2021

Опубликована: Март 1, 2024

Язык: Английский

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Photocatalytic Enantioselective Radical Cascade Multicomponent Minisci Reaction of β‐Carbolines Using Diazo Compounds as Radical Precursors

Advanced Science, Год журнала: 2024, Номер 11(25)

Опубликована: Апрель 19, 2024

Abstract Here, a photocatalytic asymmetric multicomponent cascade Minisci reaction of β‐carbolines with enamides and diazo compounds is reported, enabling an effective enantioselective radical C─H functionalization high yields enantioselectivity (up to 83% yield 95% ee). This protocol exhibits step economy, chemo‐/enantio‐selective control, good functional group tolerance, allowing access variety valuable chiral β‐carbolines. Notably, are suitable precursors in reactions. Moreover, the efficiency practicality this approach demonstrated by synthesis bioactive natural products.

Язык: Английский

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Enantioselective Hydroaminoalkylation of Azaaryl Ketones through Asymmetric Photoredox Catalysis

Organic Letters, Год журнала: 2024, Номер 26(23), С. 5037 - 5042

Опубликована: Июнь 5, 2024

An enantioselective hydroaminoalkylation of azaaryl ketones under a transition-metal-free asymmetric photoredox catalysis platform is reported. A series valuable azaarene-functionalized 1,2-amino alcohols featuring attractive quaternary carbon stereocenters have been synthesized in high yields with good to excellent enantioselectivities. The viability readily accessible N-aryl glycines as reaction partners facilitates the conjugate modification these products into important derivatives, thereby enhancing synthetic utility current approach.

Язык: Английский

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From Radical Coupling to Enantioselective Controlled Protonation: Advancing Precise Construction of Stereocenters

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

Опубликована: Янв. 23, 2025

Recent advancements in green and sustainable platforms, particularly visible light-driven photocatalysis, have spurred significant progress radical chemistry, enabling the efficient synthesis of important molecules from simple readily available feedstocks under mild conditions. However, rapid orbital flipping high reactivity radicals pose substantial challenges for achieving precise enantiocontrol stereocenter formation via coupling. In this study, we present a generic strategy that modulates elusive approach, facilitating enantiocontrollable protonation through 1,3-boron migration. We successfully developed two previously photocatalytic asymmetric transformations: de Mayo reaction utilizing energy transfer three-component reactions cyanoazaarenes initiated by single-electron transfer. Moreover, incorporation cost-effective D2O as deuterium source enhances synthetic pharmaceutical significance method, offering valuable tool future applications.

Язык: Английский

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Palladium-Catalyzed Divergent Synthesis from o-Sulfonamido Trifluoroacetophenones and 2-En-4-ynyl Carbonates

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 15, 2025

Here we present a palladium-catalyzed divergent transformative reaction between o-sulfonamido trifluoroacetophenones and 2-en-4-ynyl carbonates. A spectrum of enantioenriched 2,5-dihydrofuran-fused tetrahydroquinolines bearing either (Z)- or (E)-exocyclic double bond are constructed with moderate to high enantioselectivity from 5-aryl-substituted carbonates by tuning palladium sources, while analogous 2,3-dihydrofuran-fused products furnished using 5-alkyl-substituted ones.

Язык: Английский

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Asymmetric copper-catalyzed hydrophosphinylation of ethynylazaarenes to access P-chiral 2-azaaryl-ethylphosphine oxides

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We report a cost-effective approach for the enantioselective hydrophosphinylation of ethynylazaarenes utilizing chiral copper catalytic platform. This strategy efficiently converts racemic secondary phosphine oxides (SPOs) into P-chiral tertiary (TPOs) bearing functionalized olefin substituents with azaarene moieties, achieving high yields and exceptional enantioselectivities. These adducts serve as crucial intermediates in development valuable 1,5-hybrid P,N-ligands. The facile introduction diverse additional carbon-centered chirality through transformation moiety effectively enhances enantioselectivity asymmetric metal catalysis compared to ligands exhibiting solely P-chirality. Mechanistic investigations reveal that interaction between Cu(i) complex azaarenes promotes kinetic resolution SPOs. robustness this method is further demonstrated by its ability incorporate deuterium atoms olefins, highlighting potential relevance pharmaceutical applications.

Язык: Английский

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Recent advances in controllable/divergent synthesis

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 890 - 914

Опубликована: Май 7, 2025

The development of streamlined methodologies for the expeditious assembly structurally diverse organic architectures represents a paramount objective in contemporary synthetic chemistry, with far-reaching implications across pharmaceutical development, advanced materials innovation, and fundamental molecular science research. In recent years, controllable/divergent strategies functional molecules using common starting have garnered significant attention due to their high efficiency. This review categorizes literatures focusing on key regulatory factors product divergent formation, which controlling chemical selectivity primarily relies ligands, metal catalysts, solvents, time, temperature, acids/bases, subtle modifications substrates. To gain deeper understanding mechanisms underlying reaction activity differentiation, provides systematic analysis critical steps through specific case studies. It is hoped that synthesis concept will spark interest practitioners aficionados delve into discipline pursue novel advancements realm synthesis.

Язык: Английский

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