Triplet Energy Transfer Photocatalysis: Unlocking the Next Level

Chem, Journal Year: 2020, Volume and Issue: 6(8), P. 1888 - 1903

Published: Aug. 1, 2020

Language: Английский

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Photocatalysis in the Life Science Industry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

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Visible-light induced dearomatization reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(6), P. 2145 - 2170

Published: Jan. 1, 2022

This review provides an overview of visible-light induced dearomatization reactions classified based on the manner in which aromaticity is disrupted.

Language: Английский

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An Excitonic Perspective on Low-Dimensional Semiconductors for Photocatalysis

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(33), P. 14007 - 14022

Published: July 23, 2020

Low-dimensional semiconductors provide a marvelous platform for pursuing versatile photocatalytic solar energy conversion. Compared with the bulk counterparts, low-dimensional possess notable Coulomb-interaction-mediated excitonic effects arising from reduced dielectric screening. As consequence, excitons or bound electron–hole pairs, together charge carriers, serve as primary photoinduced energetic species. In terms of photocatalysis, exciton-based transfer establishes distinctly different mechanisms utilization beyond traditional carrier-based transfer. Moreover, owing to relationships between and play crucial role in determining quantum yields both exciton- carrier-triggered reactions. The above unique features enable optimized semiconductor-based photocatalysis be achieved by non-trivial regulation. this Perspective, we attempt an overview impacts on photocatalysis. By figuring out differences carriers degrees freedom like spin orbital, emphasize importance properties We discuss interplay charge-carrier aspects highlight necessity evaluating when dealing further review recent achievements regulating photocatalysts. conclude Perspective eye toward future challenges field.

Language: Английский

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Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes

Science, Journal Year: 2021, Volume and Issue: 371(6536), P. 1338 - 1345

Published: March 25, 2021

Heteroaromatics lured into cycloadditions The Diels-Alder reaction is widely used to produce six-membered carbon rings from alkenes and dienes. such as quinolines resemble dienes in principle, but practice their pairs of double bonds are inert toward because aromatic stabilization. Ma et al. report that by using an iridium photosensitizer, they could excite related azaarenes triplet states, thereby disrupting the aromaticity enabling intermolecular, Diels-Alder–like reactivity (see Perspective Schmidt). reactions proceeded exclusively at flanking carbons outside nitrogen-containing ring. Science , this issue p. 1338 ; see also 1313

Language: Английский

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Birch‐Type Photoreduction of Arenes and Heteroarenes by Sensitized Electron Transfer

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(40), P. 14289 - 14294

Published: Aug. 5, 2019

The direct reduction of arenes and heteroarenes by visible-light irradiation remains challenging, as the energy a single photon is not sufficient for breaking aromatic stabilization. Shown herein that accumulation two photons allows dearomatization heteroarenes. Mechanistic investigations confirm combination energy-transfer electron-transfer processes generates an arene radical anion, which subsequently trapped hydrogen-atom transfer finally protonated to form dearomatized product. photoreduction converts planar feedstock compounds into molecular skeletons are use in organic synthesis.

Language: Английский

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Recent Advances in the Construction of Spiro Compounds via Radical Dearomatization

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(21), P. 4446 - 4461

Published: July 15, 2020

Abstract The field in dearomatization of aromatic compounds for the construction spirocycle has been developed rapidly over last two decades and it provides alternative synthetic method without using extra stoichiometric amounts chemical oxidants or reductants. In addition, radical cascade reactions alkenes alkynes that produce multiple bonds one‐step are significant direct efficient building complex molecules. By combining these concepts, opens a new powerful avenue accessing These have well explored past decade. As result, we summarize recent eventful advances this growing area as review, which typical examples listed mechanism also discussed. magnified image

Language: Английский

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Energy-Transfer-Enabled Dearomative Cycloaddition Reactions of Indoles/Pyrroles via Excited-State Aromatics

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(17), P. 2510 - 2525

Published: Aug. 9, 2022

Exploring the enormous chemical space through an expedient building-up of molecular diversity is important goal organic chemistry. The development synthetic methods toward molecules with unprecedented structural motifs lays foundation for wide applications ranging from pharmaceutical chemistry to materials science. In this regard, dearomatization arenes has been recognized as a unique strategy since it provides novel retrosynthetic disconnections various spiro or fused polycyclic increased saturation and stereoisomerism. However, inherent thermodynamic challenges are associated processes. disruption aromaticity arene substrates usually requires large energy inputs, which makes harsh conditions necessary many ground-state reactions. Therefore, further expansion scope reactions remains major problem not fully solved in chemistry.The past decade witnessed tremendous progress on photocatalytic under visible light. Particularly, via transfer mechanism have unlocked new opportunities Mediated by appropriately chosen photosensitizers, aromatic can be excited. This kind precise input might make feasible some that otherwise unfavorable thermal because significant increases substrates. Nevertheless, lifetimes key intermediates energy-transfer-enabled reactions, such excited-state aromatics downstream biradical species, quite short. How regulate reactivities these transient achieve exclusive selectivity certain reaction pathway among possibilities crucial issue addressed.Since 2019, our group reported series visible-light-induced dearomative cycloaddition indole pyrrole derivatives. It was found units excited irradiation light presence suitable photosensitizer. These readily undergo [m + n] tethered unsaturated functionalities including alkenes, alkynes, N-alkoxy oximes, (hetero)arenes, vinylcyclopropanes. yield indolines pyrrolines highly strained small- and/or medium-sized rings embedded, possess bridge- cagelike topologies. Systematic mechanistic studies confirmed involvement process. Density functional theory (DFT) calculations revealed correlation between substrate structure excitation efficiency, accelerated optimization parameters. Meanwhile, DFT demonstrated competition kinetically thermodynamically controlled pathways open-shell singlet intermediates, allowed complete switches [2 2] 1,5-hydrogen atom oximes [4 naphthalene. Furthermore, ab initio dynamics (AIMD) simulations uncovered post-spin crossing dynamic effects, determine regioselectivity recombination step pyrrole-derived vinylcyclopropanes.An increasing number scientists joined research contributed more elegant examples area. mechanism, although still its infancy, exhibited great potential synthesis hardly accessed other methods. We believe future will push boundary find related disciplines.

Language: Английский

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Synthesis of Polysubstituted 2-Oxabicyclo[2.1.1]hexanes via Visible-Light-Induced Energy Transfer

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20207 - 20213

Published: Oct. 27, 2022

Synthesis of bicyclic scaffolds has attracted growing interest because they are high importance in modern pharmaceutical development. Here we report a strategy to access polysubstituted 2-oxabicyclo[2.1.1]hexanes single operation from readily accessible benzoylformate esters and bicyclo[1.1.0]butanes via visible-light-induced triplet energy transfer catalysis. The process is proposed involve formal [2π + 2σ] photocycloaddition/backbone C-H abstraction/aryl group migration sequence. A diverse range (hetero)aryl groups successfully underwent the backbone (C2) position provide previously inaccessible molecules, ester product can serve as handle for downstream manipulation, thus offering opportunities rapidly build up molecular complexity new sp3-rich chemical space.

Language: Английский

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Enantioselective [2+2]-cycloadditions with triplet photoenzymes

Nature, Journal Year: 2022, Volume and Issue: 611(7937), P. 715 - 720

Published: Sept. 21, 2022

Language: Английский

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