Energy transfer photocatalysis: exciting modes of reactivity

Chemical Society Reviews, Год журнала: 2024, Номер 53(3), С. 1068 - 1089

Опубликована: Янв. 1, 2024

Leveraging light energy to expose the ‘dark’ reactive states describes whole essence of triplet–triplet transfer. This offers an impressive opportunity conduct a multitude diverse reactions and access sought-after molecular motifs.

Язык: Английский

---

Carbene-catalyzed chirality-controlled site-selective acylation of saccharides

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 2, 2025

Acylation stands as a fundamental process in both biological pathways and synthetic chemical reactions, with acylated saccharides their derivatives holding diverse applications ranging from bioactive agents to building blocks. A longstanding objective organic synthesis has been the site-selective acylation of without extensive pre-protection alcohol units. In this study, we demonstrate that by simply altering chirality N-heterocyclic carbene (NHC) catalysts, site-selectivity saccharide reactions can be effectively modulated. Our investigation reveals intriguing selectivity shift stems combination factors, including match/mismatch inter- / intramolecular hydrogen bonding between NHC catalyst substrates. These findings provide valuable insights into design reaction engineering, highlighting potential glycoside analysis, such fluorescent labelling, α/β identification, orthogonal selective late-stage modifications. The units synthesis. Here, authors

Язык: Английский

---

Modular assembly of arenes, ethylene and heteroarenes for the synthesis of 1,2-arylheteroaryl ethanes

Nature Chemistry, Год журнала: 2024, Номер 16(10), С. 1705 - 1714

Опубликована: Июнь 27, 2024

Язык: Английский

---

Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1854 - 1941

Опубликована: Янв. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Язык: Английский

---

Nickel‐Catalyzed Highly Selective Radical C−C Coupling from Carboxylic Acids with Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 24, 2024

Controlling the cross-coupling reaction between two different radicals is a long-standing challenge due to process occurring statistically, which would lead three products, including homocoupling products and one product. Generally, selectivity achieved by persistent radical effect (PRE) that requires presence of transient radical, thus resulting in limited precursors. In this paper, highly selective alkyl with acyl construct C(sp

Язык: Английский

---

Photocatalytic Phosphine-Mediated Thioesterification of Carboxylic Acids with Disulfides

Organic Letters, Год журнала: 2023, Номер 25(44), С. 8033 - 8037

Опубликована: Окт. 27, 2023

Herein, a practical and effective synthesis of thioesters from readily available carboxylic acids odorless disulfides was developed under photocatalytic conditions. This approach involves phosphoranyl radical-mediated fragmentation to generate acyl radicals allows for incorporation both S atoms the into desired products. In addition batch reactions, continuous-flow reactor employed, enabling rapid thioester on gram scale. Preliminary experimental mechanistic studies dalcetrapib are also demonstrated.

Язык: Английский

---

Photochemical Synthesis of Thioesters from Aryl Halides and Carboxylic Acids

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(37)

Опубликована: Июнь 18, 2024

Thioesters are important in synthesis, materials science, and biology, their preparation traditionally relies on the use of disagreeable thiols. Here, we report a thiol-free protocol that stitches together widespread carboxylic acids aryl halides, producing diverse array thioesters. Crucial to this strategy is discovery tetramethylthiourea can serve as both sulfur source and, upon direct excitation by purple light, strong reductant, suitable for activating halides via single-electron transfer. Coupling resulting radicals provides an isothiouronium ion intermediate, which be attacked polar pathway, affording thioester products under mild conditions.

Язык: Английский

---

Nickel‐Catalyzed Synthesis of Thioesters from Amides and Disulfides

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(12)

Опубликована: Фев. 8, 2024

Abstract A novel nickel‐catalyzed practical and simple synthesis of thioesters from amides disulfides has been developed. Diverse substituted aromatic are capable coupling with diaryl or dialkyl via C−N/S−S bonds cleavage to produce the desirable in moderate good yields. This procedure features cheap metals, easily preparative substrates, providing a access variety without toxic thiols CO gas.

Язык: Английский

---

P^III/P^V═O Redox Catalysis Mediated Thioesterification of Carboxylic Acids with Disulfides under Air Conditions

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

Опубликована: Янв. 12, 2025

An efficient organophosphorus-catalyzed thiocarbonylation reaction of disulfides with carboxylic acids under air conditions was described. Various functional groups on and can be tolerated the present conditions, affording thioesters in good to excellent yields. This method exhibited chemoselectivity applied for late-stage functionalization drug molecules containing a acid group.

Язык: Английский

---

Unveiling Heavier Dihydropyridine Chalcogenol Esters in Metallaphotoredox Catalyst-Enabled Regioselective Hydrothio(seleno)carbonylation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Herein, aromaticity-driven thio(seleno)ester group transfer from novel 1,4-dihydropyridine thio(seleno)esters to alkene feedstocks is disclosed by merging palladium and photoredox catalysis. In this process, photoactivation of dihydropyridine integrated with regioselective hydrometalation alkenes, avoiding photoinduced Pd-C bond homolysis organopalladium intermediates. Additionally, a hydroselenocarbonylation an accomplished for the first time using bench-stable selenoester reagent. The activation mode thioesters has been illustrated detailed mechanistic studies, spectroscopic analysis, intermediate trapping, isotope labeling experiments.

Язык: Английский

---