Boryl Radical as a Catalyst in Enabling Intra‐ and Intermolecular Cascade Radical Cyclization Reactions: Construction of Polycyclic Molecules DOI
Jie Wang, Yee Lin Phang,

You‐Jie Yu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 9, 2024

Abstract Cascade radical cyclization constitutes an atom‐ and step‐economic route for rapid assembly of polycyclic molecular skeletons. Although array redox‐active metal catalysts has recently shown robust applications in enabling various catalytic cascade processes, the use free organic as catalyst, which is capable triggering strategically distinct cascades, rarely been developed. Here, we disclosed that benzimidazolium‐based N ‐heterocyclic carbene (NHC)‐boryl catalyzing reactions both intra‐ intermolecular pathways, assembling [5,5] fused bicyclic [6,6,6] tricyclic molecules, respectively. The start with chemo‐ regioselective addition boryl catalyst to a tethered alkene or alkyne moiety, followed by either intramolecular formal [3+2] [2+2+2] cycloaddition process construct bicyclo[3.3.0]octane tetrahydrophenanthridine skeletons, Eventually, β‐elimination occurs release completing cycle. High excellent diastereoselectivity achieved under substrate control.

Язык: Английский

Reactivity of oximes for diverse methodologies and synthetic applications DOI Open Access
Katie A. Rykaczewski, Emily R. Wearing, Dominique E. Blackmun

и другие.

Nature Synthesis, Год журнала: 2022, Номер 1(1), С. 24 - 36

Опубликована: Янв. 12, 2022

Язык: Английский

Процитировано

99
Photochemical Formal (4 + 2)-Cycloaddition of Imine-Substituted Bicyclo[1.1.1]pentanes and Alkenes DOI
Alexander S. Harmata,

Taylor E. Spiller,

Madison J. Sowden

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(50), С. 21223 - 21228

Опубликована: Дек. 13, 2021

Amines containing bridged bicyclic carbon skeletons are desirable building blocks for medicinal chemistry. Herein, we report the conversion of bicyclo[1.1.1]pentan-1-amines to a wide range polysubstituted bicyclo[3.1.1]heptan-1-amines through photochemical, formal (4 + 2)-cycloaddition an intermediate imine diradical. To our knowledge, this is first reported method convert bicyclo[1.1.1]pentane skeleton bicyclo[3.1.1]heptane skeleton. Hydrolysis products gives complex, sp3-rich primary amine blocks.

Язык: Английский

Процитировано

88
Photocatalytic cyclization of nitrogen-centered radicals with carbon nitride through promoting substrate/catalyst interaction DOI Creative Commons

Ming-Cheng Yang,

Ronghong Lian,

Xirui Zhang

и другие.

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Авг. 20, 2022

Abstract The use of metal-free carbon nitride and light to drive catalytic transformations constitutes a sustainable strategy for organic synthesis. At the moment, enhancing intrinsic activity CN catalysts by tuning interfacial coupling between catalyst substrate remains challenging. Herein, we demonstrate that urea-derived with abundant −NH 2 groups relative positive charged surface could effectively complex deprotonated anionic intermediate improve adsorption reactants on surface. decreased oxidation potential upshift in its highest occupied molecular orbital position make electron abstraction kinetics more energetically favorable. prepared is thus utilized photocatalytic cyclization nitrogen-centered radicals synthesis diverse pharmaceutical-related compounds (33 examples) high reusability, which shows competent performance homogeneous catalysts.

Язык: Английский

Процитировано

64
Diradical Generation via Relayed Proton-Coupled Electron Transfer DOI
Qianqian Shi, Zhipeng Pei, Jinshuai Song

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(7), С. 3137 - 3145

Опубликована: Фев. 8, 2022

Diradical generation followed by radical–radical cross-coupling is a powerful synthetic tool, but its detailed mechanism has yet to be established. Herein, we proposed and confirmed new model named relayed proton-coupled electron transfer (relayed-PCET) for diradical generation, which could open door reactions. Quantum mechanics calculations were performed on selected carbene-mediated reaction designed model, the exact electronic structural changes during radical processes have been observed first time.

Язык: Английский

Процитировано

55
Synthesis of medium-sized benzo[b]azocines and benzo[b]azonines by photoinduced 8-/9-endo sulfonyl-cyclization DOI
Kai Sun, Dongyang Zhao, Quanxin Li

и другие.

Science China Chemistry, Год журнала: 2023, Номер 66(8), С. 2309 - 2316

Опубликована: Июль 24, 2023

Язык: Английский

Процитировано

40
Electrophotocatalytic tri- or difluoromethylative cyclization of alkenes DOI
Danna Chen,

Xuege Yang,

Dongyin Wang

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(10), С. 2482 - 2490

Опубликована: Янв. 1, 2023

Photoelectrocatalysis is mild yet potent and this work unlocks the potential of unactivated alkenes for oxidant-free oxidative cyclization alkenes.

Язык: Английский

Процитировано

33
An in-situ Generated Proton Initiated Aromatic Fluoroalkylation via Electron Donor-Acceptor Complexes Photoactivation DOI

Panyi Huang,

Chun Lv,

Haijing Song

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(12), С. 7198 - 7205

Опубликована: Янв. 1, 2024

In situ -generated protonated aromatic hydrocarbons overcome their intrinsic electronic properties to serve as catalytic electron acceptors, avoiding the use of photocatalysts, metals, and redox reagents achieve fluoroalkylation.

Язык: Английский

Процитировано

13
Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors DOI
Qiao Sun, Shaopeng Wang, Yuan Xu

и другие.

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

Процитировано

1
Recent Advances in Photoredox/Nickel Dual-Catalyzed Difunctionalization of Alkenes and Alkynes DOI Open Access
Lei Xu, Fang Wang, Fan Chen

и другие.

Chinese Journal of Organic Chemistry, Год журнала: 2022, Номер 42(1), С. 1 - 1

Опубликована: Янв. 1, 2022

The merger of visible-light photoredox catalysis and nickel makes it possible to forge challenging chemical bonds under mild conditions.Nevertheless, most these transformations only construct a single carbon-carbon bond or carbon-heteroatom in one operation.In recent years, photoredox/nickel dual has attracted widespread attention the field catalytic difunctionalization alkenes alkynes.The synergistic cascade mode enables construction multiple pot, providing mild, efficient selective protocol for rapid assembly complex structural motifs.The latest progress dual-catalyzed reactions olefins alkynes is summarized.

Язык: Английский

Процитировано

37
Intramolecular, Visible-Light-Mediated Aza Paternò-Büchi Reactions of Unactivated Alkenes DOI
Dominique E. Blackmun, Stephen A. Chamness, Corinna S. Schindler

и другие.

Organic Letters, Год журнала: 2022, Номер 24(16), С. 3053 - 3057

Опубликована: Апрель 19, 2022

Azetidines are of particular interest in medicinal chemistry for their favorable properties, including increased resistance to oxidative metabolism and lower lipophilicity. The recent development [2 + 2] reactions has significantly expanded the limited repertoire methods azetidine synthesis, but access more complex architectures still requires further development. Herein, we report a visible-light-enabled intramolecular cycloaddition unactivated alkenes that proved previously unreactive tricyclic azetidines with 3D structures high levels saturation.

Язык: Английский

Процитировано

31