Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7214 - 7261

Опубликована: Май 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Язык: Английский

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Photocatalytic Synthesis of Indanone, Pyrone, and Pyridinone Derivatives with Diazo Compounds as Radical Precursors

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1393 - 1398

Опубликована: Фев. 12, 2024

We disclose herein a photocatalytic radical cascade cyclization of diazoalkanes for the divergent synthesis important carbocycles and heterocycles. Under optimal reaction conditions, various indanone, pyrone, pyridinone derivatives can be obtained in moderate to good yields. Mechanistic experiments support formation carbon-centered radicals from through proton-coupled electron transfer process. Scale-up using continuous flow technology useful downstream application formed heterocycles further render strategy attractive valuable.

Язык: Английский

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Semiheterogeneous Photoredox Catalysis: Synthesis of 3-Sulfonylquinolines via Radical Multicomponent Cascade Annulation

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13782 - 13788

Опубликована: Сен. 2, 2024

An efficient photocatalytic protocol combining heterogeneous semiconductors as photocatalysts and NHPI a redox reagent was disclosed. Under this protocol, 3-sulfonylquinolines were formed in up to 92% yield via multicomponent radical cascade annulation. Good substituent tolerance gram-scale reaction showed the potential fine chemicals modification pharmaceutical synthesis.

Язык: Английский

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General Synthesis of N-Alkylindoles from N,N-Dialkylanilines via [4 + 1] Annulative Double C–H Functionalization

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26540 - 26544

Опубликована: Ноя. 29, 2023

Strategies enabling the construction of indoles and novel polycyclic heterocycles from simple building blocks streamline syntheses in synthetic medicinal chemistry. Herein, we report a C–H functionalization approach to N-alkylindoles proceeding via double, site-selective C(sp3)–H/C(sp2)–H [4 + 1] annulation readily accessed N,N-dialkylanilines. This protocol features hydrogen atom transfer by tuned N-tBu amidyl radical addition sulfonyl diazo coupling partner, which promotes highly homolytic aromatic substitution (hetero)aromatic core. Mild decarboxylation product enables overall introduction carbyne equivalent into N,N-dialkylaniline scaffold. Furthermore, site-selectivity mild conditions indolization facilitate direct access N-alkyl indole scaffolds late-stage (LSF) settings.

Язык: Английский

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Photocatalytic Synthesis of Isoquinolinediones via the Cascade Reaction of N-Alkyl-N-methylacrylamides with Diazo Compounds

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Carbon radicals generated from acceptor diazo compounds prefer to add electron-rich olefins and heteroarenes due their containing electron-withdrawing groups. Herein, a cascade reaction of with electron-deficient is developed. In the presence visible light Ru catalyst, generate carbon via proton-coupled electron transfer process, followed by addition various N-alkyl-N-methylacrylamides subsequent cyclization give series acyl-substituted isoquinolinediones.

Язык: Английский

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Photolytic Access to Oxaspirodecanes and Chromenes from Vinyldiazo Ester Cycloaddition with p-Quinones: A Vinylcarbene Is Not Involved

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

Опубликована: Март 26, 2025

Synthetic methods that provide access to skeletally diverse heterocyclic motifs are poised accelerate drug discovery and streamline the synthesis of advanced intermediates materials. However, development such synthetic necessitates leveraging previously unexplored mechanistic pathways. We report herein an efficient blue light-emitting diode light-induced reaction vinyldiazoacetates quinones produces spirocyclic dihydrofurans, featuring synthetically challenging oxaspiro[4,5]decane core numerous medicinal agents, agrochemicals, natural products. In a departure from well-established photochemical reactivity diazo compounds, these reactions do not involve vinylcarbene formed by photolytic dinitrogen extrusion. Instead, they result photoexcitation quinone its triplet state with subsequent energy transfer vinyldiazo ester. The addition vinylogous carbon vinyldiazoacetate oxygen affords diradical collapses dihydrofuran upon loss dinitrogen. A strain release-driven Bro̷nsted acid-catalyzed rearrangement products unravels fused bicyclic ring system equally medicinally valuable chromenes, enabling facile skeletal diversification important motifs.

Язык: Английский

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Hybrid Carbon Nitride/Cobalt Phthalocyanine Nanocomposites for Efficient Photocatalytic Hydrogen Generation

ACS Applied Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 4, 2025

Язык: Английский

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Photocatalytic C−C bond formation and cleavage reactions based on graphitic carbon nitride semiconductor materials

Tetrahedron, Год журнала: 2025, Номер unknown, С. 134651 - 134651

Опубликована: Апрель 1, 2025

Язык: Английский

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Photocatalyst‐Free Visible Light‐Induced C(sp²)−H Arylation of Quinoxalin‐2(1H)‐ones and Coumarins

Chemistry - A European Journal, Год журнала: 2024, Номер 30(44)

Опубликована: Июнь 3, 2024

Herein, we describe a visible light-induced C(sp

Язык: Английский

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Visible-Light-Promoted C3-Sulfenylindoles with Arylsulfonyl Chlorides via Electron Donor–Acceptor Complex

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(11), С. 7591 - 7597

Опубликована: Май 9, 2024

In this study, we present an efficient approach for the synthesis of 3-sulfenyl indoles through electron donor–acceptor (EDA) complex-promoted photoreaction. This sulfenylation reaction leverages sulfonyl chlorides as sulfur source and employs PPh3 reductant without need any transition-metal catalyst or photocatalyst. At same time, relaxation process excited EDA complex was theoretically investigated at method multiconfiguration second-order perturbation//complete active space self-consistent field/PCM level theory, which involves π bond injecting to antibonding orbital S–Cl in arylsulfonyl chlorides.

Язык: Английский

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