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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Overall photosynthesis of H2O2 by an inorganic semiconductor

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 24, 2022

Abstract Artificial photosynthesis of H 2 O using earth-abundant water and oxygen is a promising approach to achieve scalable cost-effective solar fuel production. Recent studies on this topic have made significant progress, yet are mainly focused organic polymers. This set photocatalysts susceptible potent oxidants (e.g. hydroxyl radical) that inevitably formed during generation. Here, we report an inorganic Mo-doped faceted BiVO 4 (Mo:BiVO ) system resistant radical oxidation exhibits high overall efficiency among photocatalysts, with apparent quantum yield 1.2% solar-to-chemical conversion 0.29% at full spectrum, as well 5.8% 420 nm. The surface-reaction kinetics selectivity Mo:BiVO were tuned by precisely loading CoO x Pd {110} {010} facets, respectively. Time-resolved spectroscopic investigations photocarriers suggest depositing select cocatalysts distinct facet tailored the interfacial energetics between facets enhanced charge separation in , therefore overcoming key challenge developing efficient photocatalysts. generation achieved delicate design catalyst spatial electronic structures sheds light applying robust particulate artificial .

Language: Английский

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Scaffold hopping by net photochemical carbon deletion of azaarenes

Science, Journal Year: 2022, Volume and Issue: 376(6592), P. 527 - 532

Published: April 28, 2022

Discovery chemists routinely identify purpose-tailored molecules through an iterative structural optimization approach, but the preparation of each successive candidate in a compound series can rarely be conducted manner matching their thought process. This is because many necessary chemical transformations required to modify cores straightforward fashion are not applicable complex contexts. We report method that addresses one facet this problem by allowing hop directly between chemically distinct heteroaromatic scaffolds. Specifically, we show selective photolysis quinoline

Language: Английский

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Energy transfer photocatalysis: exciting modes of reactivity

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1068 - 1089

Published: Jan. 1, 2024

Leveraging light energy to expose the ‘dark’ reactive states describes whole essence of triplet–triplet transfer. This offers an impressive opportunity conduct a multitude diverse reactions and access sought-after molecular motifs.

Language: Английский

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Photochemical single-step synthesis of β-amino acid derivatives from alkenes and (hetero)arenes

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(10), P. 1174 - 1184

Published: Aug. 1, 2022

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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Strain-Release Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 20716 - 20732

Published: Sept. 15, 2023

The concept of strain in organic compounds is as old modern chemistry and was initially introduced to justify the synthetic setbacks along synthesis small ring systems (pars construens strain). In last decades, chemists have developed an arsenal strain-release reactions destruens strain) which can generate─with significant driving force─rigid aliphatic that act three-dimensional alternatives (hetero)arenes. Photocatalysis added additional dimension processes by leveraging energy photons create chemical complexity under mild conditions. This perspective presents latest advancements photocatalysis─with emphases on mechanisms, catalytic cycles, current limitations─the unique architectures be produced, possible future directions.

Language: Английский

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ortho-Selective Dearomative [2π + 2σ] Photocycloadditions of Bicyclic Aza-Arenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12324 - 12332

Published: May 26, 2023

Dearomative photocycloadditions are valuable chemical transformations, serving as an efficient platform to create three-dimensional molecular complexity. However, the photolability of original addition product especially within context ortho cycloadditions often causes undesired consecutive rearrangements, rendering these cycloadducts elusive. Herein, we report ortho-selective intermolecular photocycloaddition bicyclic aza-arenes including (iso)quinolines, quinazolines, and quinoxalines by utilizing a strain-release approach. With bicyclo[1.1.0]butanes coupling partners, this dearomative [2π + 2σ] cycloaddition enables straightforward construction C(sp3)-rich bicyclo[2.1.1]hexanes directly connected N-heteroarenes. Photophysical experiments DFT calculations revealed origin selectivity indicate that, in originally proposed energy transfer or direct excitation pathways, chain reaction mechanism is operative depending on conditions.

Language: Английский

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General heterostructure strategy of photothermal materials for scalable solar-heating hydrogen production without the consumption of artificial energy

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 9, 2022

Solar-heating catalysis has the potential to realize zero artificial energy consumption, which is restricted by low ambient solar heating temperatures of photothermal materials. Here, we propose concept using heterostructures black materials (such as Bi2Te3) and infrared insulating (Cu) elevate temperatures. Consequently, heterostructure Bi2Te3 Cu (Bi2Te3/Cu) increases 1 sun-heating temperature from 93 °C 317 achieving synergy 89% absorption 5% radiation. This strategy applicable for various raise Ti2O3, Cu2Se, Cu2S 295 °C, 271 248 respectively. The Bi2Te3/Cu-based device able heat CuOx/ZnO/Al2O3 nanosheets 305 under sun irradiation, this system shows a sun-driven hydrogen production rate 310 mmol g-1 h-1 methanol water, at least 6 times greater than that all solar-driven systems date, with 30.1% solar-to-hydrogen efficiency 20-day operating stability. Furthermore, enlarged m2 generate 23.27 m3/day outdoor sunlight irradiation in spring, revealing its industrial manufacture.

Language: Английский

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Cascade asymmetric dearomative cyclization reactions via transition-metal-catalysis

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(3), P. 203 - 216

Published: March 14, 2022

Language: Английский

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