Photoinduced Trifluoromethylselenolation of Aryl Halides with [Me4N][SeCF3] DOI
Fei Li, Xue Han, Ziang Xu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(43), P. 7884 - 7889

Published: Oct. 25, 2023

A visible-light-induced metal-free trifluoromethylselenolation of aryl iodides and bromides with [Me4N][SeCF3] is described. The reaction was conducted at ambient temperature by successfully harnessing the light-sensitive SeCF3 reagent. Mechanistically, EDA complexes between halide -SeCF3 anion or base might be formed excited light, which subsequently undergo intracomplex SET processes to generate •SeCF3 radicals as key intermediates, allowing a convenient green access various trifluoromethyl selenoethers.

Language: Английский

A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes DOI
Juan D. Lasso, Durbis J. Castillo‐Pazos, Jan Michael Salgado

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2583 - 2592

Published: Jan. 17, 2024

Catalytic electron donor–acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- ruthenium-based photoredox synthetic methods. Yet, these remain underexplored reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report novel EDA complex employing tris(4-methoxyphenyl) amine catalytic donor for sulfonylation alkenes using inexpensive readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, both redox-neutral net-reductive functionalization more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, sulfamoylation activated unactivated alkynes.

Language: Английский

Citations

43
Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes DOI Creative Commons
Anthony J. Fernandes, Rahul Giri, K. N. Houk

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Jan. 29, 2024

Abstract We highlight key contributions in the field of direct radical C Ar − H (hetero)aromatic functionalization involving fluorinated radicals. A compilation Functional Group Transfer Reagents and their diverse activation mechanisms leading to release radicals are discussed. The substrate scope for each is analyzed classified into three categories according electronic properties substrates. Density functional theory computational analysis provides insights chemical reactivity several through electrophilicity nucleophilicity parameters. Theoretical reduction potentials also highlights remarkable correlation between oxidizing ability. It established that highly (e.g. ⋅OCF 3 ) capable engaging single‐electron transfer (SET) processes rather than addition, which good agreement with experimental literature data. scale, based on barrier addition these benzene elaborated using high accuracy DLPNO‐(U)CCSD(T) method.

Language: Английский

Citations

21
Visible photons as ideal reagents for the activation of coloured organic compounds DOI Creative Commons
Lorenzo Di Terlizzi, Luca Nicchio,

Stefano Protti

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975

Published: Jan. 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.

Language: Английский

Citations

12
Mechanochemical-assisted decarboxylative sulfonylation of α,β-unsaturated carboxylic acids with sodium sulfinate salts DOI

Barakha Saxena,

Roshan I. Patel,

Shruti Sharma

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(5), P. 2721 - 2729

Published: Jan. 1, 2024

Herein, we report a mechanochemical-assisted decarboxylative sulfonylation of α,β-unsaturated carboxylic acids with sodium sulfinate salts using potassium iodide as an activator under water-assisted grinding conditions.

Language: Английский

Citations

11
Dioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation DOI Creative Commons
Jialiang Wei,

Junhong Meng,

Caifang Zhang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 29, 2024

Abstract The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities for synthetic chemistry. However, these strategies often require an inert atmosphere to maintain high efficiency. Herein, we develop EDA complex photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation traditional systems and enables aerobic oxygenation reactions dioxygen activation. mild oxidation transfers electrons from donor effective catalytic acceptor upon visible light irradiation, are subsequently captured by molecular oxygen form superoxide radical ion, as demonstrated specific fluorescent probe, dihydroethidine (DHE). Furthermore, this visible-light mediated oxidative protocol is successfully applied in boronic acids. We believe that activation strategy enabled not only provides a practical approach but also promotes design application photocatalysis under ambient conditions.

Language: Английский

Citations

11
Recent Advances and Development in Visible‐Light‐Mediated Glycosylation: An Expanding Research Area in Glycochemistry DOI

Zanjila Azeem,

Pintu Kumar Mandal

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(17), P. 2818 - 2849

Published: July 7, 2023

Abstract In the last fifteen years, development of visible‐light photocatalysis, metal/photoredox dual catalysis has become forefront as a new paradigm in organic synthesis well carbohydrate chemistry. It led to discovery unprecedented transformations and also improvement known reactions under mild conditions, employing simple household light sources bench‐stable precursors, which meet requirements green chemistry sustainable excellent yield stereocontrol. general sense, exploitation photoredox hinges on capability photocatalyst or redox mediator transform visible into chemical energy via photo‐irradiated SET (single electron transfer), PET (photoinduced HAT (hydrogen atom XAT (halogen transfer) potentially unlock unique reaction pathways, thereby generating diverse array reactive intermediates. view type, mechanism, status, this review will systematically summarize latest advances visible‐light‐promoted photocatalytic glycosylation reactions, are driven by single photoactivity donor‐acceptor (EDA) complexes.

Language: Английский

Citations

20
Visible light-assisted chemistry of vinyl azides and its applications in organic synthesis DOI

Barakha Saxena,

Roshan I. Patel,

Jaya Tripathi

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(23), P. 4723 - 4743

Published: Jan. 1, 2023

Vinyl azides have emerged as highly versatile precursors in organic synthesis due to their rich reactivity driven by the excellent leaving-group ability of molecular nitrogen. Over years, significant advancement has been achieved manipulation vinyl for construction C-C and C-X bonds. Typical methods involve application transition metals strong oxidants conversion into useful compounds employing harsh reaction conditions coupled with intense product purification. In this regard, visible light chemistry become one most exciting fields being mild, sustainable, often orthogonal conventional approaches. Visible light-induced reactions involving generate either 2H-azirines or iminyl radicals key intermediates, which may undergo further transformations form desired cyclic acyclic products. Herein, we provide synthetic transient intermediates biological significance under photocatalysis. We classified review two parts: (i) formation an radical intermediate (ii) 2H-azirine intermediate-based reactions.

Language: Английский

Citations

17
Photoinduced catalyst-free difluoromethylation–cyclization of indole derivatives via electron donor–acceptor complexes under visible light DOI

Hong-Xian Jin,

Yuping Zhu,

Jie Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(20), P. 5762 - 5768

Published: Jan. 1, 2024

A novel catalyst-free photoinduced difluoromethylation–cyclization via electron donor–acceptor (EDA) complexes was developed for the synthesis of fluorinated compounds.

Language: Английский

Citations

6
Visible light-induced bromine radical enhanced hydrogen atom transfer (HAT) reactions in organic synthesis DOI Creative Commons

Barakha Saxena,

Roshan I. Patel,

Anuj Sharma

et al.

RSC Sustainability, Journal Year: 2024, Volume and Issue: 2(8), P. 2169 - 2189

Published: Jan. 1, 2024

This review describes the recent advancements in visible light-induced bromine radical enhanced hydrogen atom transfer (HAT) reactions organic synthesis.

Language: Английский

Citations

5
Visible-Light-Induced Domino Perfluoroalkylation/Cyclization to Access Perfluoroalkylated Quinazolinones by an EDA Complex DOI
Fei Meng,

Yangyang Cui,

Wen Xu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6884 - 6888

Published: Aug. 1, 2024

The electron donor–acceptor (EDA) complexes have been extensively studied, which formed an electronically excited state, obviating the need for exogenous photocatalyst. Herein, we report a mild and efficient strategy photoinduced radical domino perfluoroalkylation/cyclization using N,N,N′,N′-tetramethylethane-1,2-diamine (TMEDA) as donor. This protocol could be well expanded to access various polycyclic quinazolinones containing perfluoroalkyl groups, exhibiting photocatalyst-free, good functional group tolerance, environmentally friendly features.

Language: Английский

Citations

5