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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Advances in heterocycle synthesis through photochemical carbene transfer reactions

Chemical Communications, Год журнала: 2024, Номер 60(16), С. 2125 - 2136

Опубликована: Янв. 1, 2024

In this feature article, we focus on the photochemical strategy for construction of heterocyclic skeletons, specifically highlighting methods that employ visible light-promoted carbene transfer reactions.

Язык: Английский

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Visible photons as ideal reagents for the activation of coloured organic compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 4926 - 4975

Опубликована: Янв. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

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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High‐Density, Crosstalk‐Free, Flexible Electrolyte‐Gated Synaptic Transistors Array via All‐Photolithography for Multimodal Neuromorphic Computing

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Abstract High‐density bio‐electrolyte‐gated synaptic transistors (BEGTs) array are promising for constructing neuromorphic computing architectures. Due to the bulk ion conductivity and crack sensitivity of electrolyte film, patterning is an indispensable route prevent spatial crosstalk improve flexibility device array. However, susceptibility bio‐electrolyte organic solvents poses challenges in developing reliable all‐photolithography techniques fabricating scalable, patterned, high‐density BEGTs This study introduces method that adopts a photo‐crosslinker‐enabled create (11846 devices per cm 2 ) multimodal demonstrates essential behaviors without inter‐device maintains its flexibility, enduring 200 bending cycles at 6 mm radius significant performance degradation. Meanwhile, exhibits behavior, not only successfully mimicking biological visual memory system sensing processing images but also proving highly accurate classifying handwritten digits, making it suitable systems. work offers dependable strategy scalable stable fabrication array, providing valuable insights advancing artificial

Язык: Английский

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Emerging progress: photochemical transformation of nitroso compounds

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Июль 17, 2024

Язык: Английский

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Fluoroalkylacylsilanes as Novel Ambiphilic Donor–Acceptor Carbene Precursors

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

ConspectusCarbenes, as highly reactive intermediates, have emerged pivotal tools in organic synthesis, catalysis, and materials science due to their versatile reactivity broad applicability. Among the diverse classes of carbenes, donor-acceptor carbenes (DACs) attracted significant attention owing unique electronic properties exceptional reaction selectivity. The distinctive DACs arises from synergistic interplay between electron-withdrawing electron-donating groups attached carbene center, enabling a wide array transformations. These attributes established indispensable building blocks for constructing complex molecular architectures achieving precise control over chemical transformation.This Account highlights our recent advancements development fluoroalkylacylsilanes novel precursors DACs. Under photocatalytic conditions, these generate fluoroalkyl siloxycarbenes via radical Brook rearrangement. group, known its strong properties, imparts electrophilic characteristics, while siloxyl group stabilizes center. Together, functionalities render ideal candidates generation DACs, providing platform range transformations, including cycloadditions, bond insertions, construction new structures.First, we developed visible-light-induced, organocatalyzed [2 + 1] cyclization alkynes trifluoroacetylsilanes, leading synthesis cyclopropenols. Mechanistic studies provided compelling evidence involvement triplet intermediates this reaction, demonstrating utility functionalized cyclic compounds. Second, explored cyclopropanation reactions elucidated diastereoselective transfer trifluoroacetylsilane-derived alkenes. Density functional theory (DFT) calculations revealed key insights into origins observed diastereoselectivity, offering molecular-level understanding stereochemical outcomes. Additionally, extended scope include organoboronic esters, divergent ketones. By modulating situ-generated organoboronate complexes─formed through with esters─we achieved selective both fluorine-maintaining defluorinated This transition-metal-free approach is operationally simple compatible substrates, aryl, alkenyl, alkyl boronic esters. Beyond C-B functionalization, applied C(sp2)-H functionalization 1,3-azoles. investigations suggest that success stems dual role trifluoroacetylsilanes under conditions: they not only participate but also produce biradicals facilitate ring-opening aromatization fused cyclopropanes.We anticipate work on ambiphilic will lay groundwork further use acylsilanes chemistry. developments are expected inspire strategies design expand silanes synthetic opening avenues intricate architectures.

Язык: Английский

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Light-induced arylation (alkylation) of N-sulfonylhydrazones with boronic acids

Chemical Communications, Год журнала: 2024, Номер 60(20), С. 2796 - 2799

Опубликована: Янв. 1, 2024

We report light-induced arylation (alkylation) for the synthesis of diarylmethanes, bis(diarylmethyl)benzenes, arylalkylmethanes, and triarylmethanes from readily accessible N -sulfonylhydrazones aryl/alkylboronic acids with aid Cs 2 CO 3 .

Язык: Английский

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Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo‐Driven Sequential Sigmatropic Rearrangement

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(24)

Опубликована: Апрель 8, 2024

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α-aryl α-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation involved with 1,6-dipolar intermediate quadruple sigmatropic rearrangements, successfully developed. In this transformation, cleavage four bonds recombination five were implemented in one operational step. This protocol provided modular tool constructing amines, pyrazoles α-alkynyl-α-diazoketones one-pot manner. The results mechanistic investigation indicated that plausible reaction path underwent 1,6-sigmatropic rearrangement instead 1,5-sigmatropic rearrangement.

Язык: Английский

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Lighting the way to diverse cyclic architectures: expanding the horizons with photogenerated ketenes in sustainable chemistry

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(18), С. 4474 - 4487

Опубликована: Янв. 1, 2023

Photogenerated ketenes simplify and accelerate the synthesis of diverse cyclic architectures demonstrate their promising applications in flow chemistry.

Язык: Английский

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