Direct C(sp³)–H Arylation of Unprotected Benzyl Anilines and Alkylarenes by Organocatalysis under Visible Light

Organic Letters, Год журнала: 2024, Номер 26(1), С. 304 - 309

Опубликована: Янв. 2, 2024

Reported herein is direct C(sp3)–H arylation of unprotected benzyl anilines and alkylarenes via consecutive photoinduced electron transfer by visible light irradiation. Reductive quenching cycles radical–radical cross-coupling were involved, paramagnetic resonance experiments provide evidence for the formation radical intermediates formed in situ. The protocol highlights transition metal free, external oxidant broad substrate scope, high efficiency (>60 examples, up to 96%).

Язык: Английский

---

Transition-Metal-Free Anti-Markovnikov Hydroarylation of Alkenes with Aryl Chlorides through Consecutive Photoinduced Electron Transfer

Organic Letters, Год журнала: 2024, Номер 26(6), С. 1265 - 1270

Опубликована: Фев. 6, 2024

The hydroarylation of alkenes has emerged as a powerful strategy for arene functionalization. However, aryl chlorides remain large challenge in this type reaction due to the chemical inertness C(sp2)–Cl bond and high negative reduction potential. Herein, we report an anti-Markovnikov radical with via visible-light photoredox catalysis. key reactive radicals can be efficiently achieved from by consecutive photoinduced electron transfer. This transition-metal-free protocol features mild conditions, wide substrate scope, functional group tolerance, producing diverse range linear alkylarenes moderate good yields. is proposed proceed through radical-polar crossover pathway.

Язык: Английский

---

Low-power, non-coherent light-triggered two-photon absorption via extending the lifetime of the transition state

Coordination Chemistry Reviews, Год журнала: 2024, Номер 511, С. 215868 - 215868

Опубликована: Апрель 22, 2024

Язык: Английский

---

Organic super-reducing photocatalysts generate solvated electrons via two consecutive photon induced processes

Chemical Science, Год журнала: 2024, Номер 15(36), С. 14739 - 14745

Опубликована: Янв. 1, 2024

The strong photoreducing abilities of the investigated TADF chromophores is result photogeneration solvated electrons in a consecutive two-photon induced mechanism (ConPies).

Язык: Английский

---

Site-Selective Pyridine Carbamoylation Enabled by Consecutive Photoinduced Electron Transfer

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 15521 - 15527

Опубликована: Окт. 4, 2024

Язык: Английский

---

Visible-Light Photoredox-Catalyzed Direct Carboxylation of Tertiary C(sp³)–H Bonds with CO₂: Facile Synthesis of All-Carbon Quaternary Carboxylic Acids

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Окт. 7, 2024

Direct carboxylation of C–H bonds with CO2 represents an attractive strategy to synthesize valuable carboxylic acids high atom, step, and redox economy. Although great progress has been achieved in this field, catalytic tertiary C(sp3)–H still remains challenging due their inherent inertness significant steric hindrance. Herein, we report a direct benzylic via visible-light photoredox catalysis. Various all-carbon quaternary acids, which are importance medicinal chemistry, successfully obtained yields. This is characterized by good functional group tolerance, broad substrate scope, mild operational conditions. Furthermore, our methodology enables the efficient rapid synthesis key drug or bioactive molecules, such as carbetapentane, caramiphen, PRE-084 (σ1 receptor agonist), facilitates various functionalizations C(sp2)–H using directing ability target thus highlighting its practical applications. Mechanistic studies indicate that carbanion, serves intermediate react CO2, catalytically generated single electron reduction radical through consecutive photoinduced transfer process.

Язык: Английский

---

Generation of Thioxanthone Hydrogen Anion by Double Photoreduction and Uses for Catalytic Photoreductions

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13588 - 13596

Опубликована: Окт. 9, 2023

Anions are the reduced form of precatalysts that a special type photoredox catalyst, unlike traditional iridium or ruthenium complexes. Among them, radical anions often have much shorter excited-state lifetimes because fast nonradiative decay. Herein, we report discovery thioxanthone hydrogen anion (5), super-reducing photocatalyst with long lifetime (Eox* = −2.74 V vs SCE, τS 4.1 ns). Using 5 as catalytic reductant, developed series photoreductions, including hydrogenation, reductive dehalogenation, deoxygenative and deoxygenation, thereby demonstrating feasibility 2e– consecutive photoinduced electron transfer (ConPET) strategy versatility catalyst.

Язык: Английский

---

Electroreductive Ring-Opening Carboxylation of 1,3-Oxazolidin-2-ones with CO₂ for Accessing β-Amino Acids

Organic Letters, Год журнала: 2024, Номер 26(2), С. 542 - 546

Опубликована: Янв. 8, 2024

Electrocarboxylation of the C(sp3)–O bond in 1,3-oxazolidin-2-ones with CO2 to achieve β-amino acids is developed. The C–O substrates can be selectively cleaved via single electron transfer on surface a cathode or through CO2• – intermediate under additive-free conditions. A great diversity obtained moderate excellent yield and readily converted various biologically active compounds.

Язык: Английский

---

Recent Advances in Single-Electron Reduction-Induced Ring Opening of N-Acyl Cyclic Amines

Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Abstract Cyclic amines represent ubiquitous structural motifs in organic chemistry, prominently featured natural products and pharmaceuticals. The development of synthetic methodologies targeting cyclic has attracted considerable interest, given their significance medicinal chemistry. These transformations can be broadly categorized into two main types: (1) peripheral modification (2) skeletal remodeling. Recent advancements late-stage C–H functionalization have showcased the potential strategies. Conversely, remodeling, particularly through ring opening amines, emerged as a powerful approach to access structurally diverse amines. Ring initiated by C–N bond cleavage, predominantly relies on two-electron mechanisms. Strained readily undergo such transformations, while those with larger-membered ring, like pyrrolidines, present greater challenges. Oxidative von Braun-type approaches facilitated heterolytic offering broad applicability across various In contrast, reductive approaches, which enable homolytic provide unique radical-mediated transformations. This short review highlights recent progress single electron reduction induced ring-opening methodologies, focusing α-aminoketyl radical generation for selective amide cleavage. Advances aziridines, azetidines, other are discussed, along implications future prospects. 1 Introduction 2 Opening Aziridines 2.1 Hydrogenation Alkylation 2.2 Isomerization 2.3 Arylation 3 Azetidines 4 Pyrrolidines Other Amines 5 Conclusion Outlook

Язык: Английский

---

Catalytic transformation of carbon dioxide into seven-membered heterocycles and their domino transformation into bicyclic oxazolidinones

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

Опубликована: Фев. 5, 2025

Converting carbon dioxide (CO2) into valuable heterocycles is of great synthetic value but usually limited to five- and six-membered ring compounds. Here, we report a catalytic approach for transforming this renewable seven-membered using double-stage approach, combining silver-catalyzed alkyne/CO2 coupling subsequent base-catalyzed ring-expansion. This methodology avoids the formation thermodynamically more stable, smaller-ring by-products has good functional group tolerance. The application these larger-ring cyclic carbonates further demonstrated by showing their unique ability serve as synthons preparation bicyclic oxazolidinone pharmacores through an intramolecular domino sequence that involves transient ketimine group, various other intermolecular transformations. results described herein significantly expand on use CO2 cheap versatile feedstock generating elusive pharmaceutically relevant authors heterocycles, expansion.

Язык: Английский

---