Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
Successive energy-transfer-mediated dearomative [2π + 2σ] cycloaddition/1,6-HAT cascade reaction of quinolines with bicyclo[1.1.0]butanes provides a facile synthesis pyridine-fused 3D complicated molecules.
Язык: Английский
Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2145 - 2170
Опубликована: Янв. 1, 2022
This review provides an overview of visible-light induced dearomatization reactions classified based on the manner in which aromaticity is disrupted.
Язык: Английский
Процитировано
226
Chemical Society Reviews, Год журнала: 2024, Номер 53(3), С. 1068 - 1089
Опубликована: Янв. 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.
Язык: Английский
Процитировано
136
Accounts of Chemical Research, Год журнала: 2022, Номер 55(17), С. 2510 - 2525
Опубликована: Авг. 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.
Язык: Английский
Процитировано
130
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(22), С. 12324 - 12332
Опубликована: Май 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.
Язык: Английский
Процитировано
121
Chemical Reviews, Год журнала: 2024, Номер 124(3), С. 1122 - 1246
Опубликована: Янв. 2, 2024
Dearomatization reactions have become fundamental chemical transformations in organic synthesis since they allow for the generation of three-dimensional complexity from two-dimensional precursors, bridging arene feedstocks with alicyclic structures. When those processes are applied to pyridines, quinolines, and isoquinolines, partially or fully saturated nitrogen heterocycles formed, which among most significant structural components pharmaceuticals natural products. The inherent challenge lies low reactivity heteroaromatic substrates, makes dearomatization process thermodynamically unfavorable. Usually, connecting event irreversible formation a strong C–C, C–H, C–heteroatom bond compensates energy required disrupt aromaticity. This aromaticity breakup normally results 1,2- 1,4-functionalization heterocycle. Moreover, combination these subsequent tandem stepwise protocols allows multiple heterocycle functionalizations, giving access complex molecular skeletons. aim this review, covers period 2016 2022, is update state art nucleophilic dearomatizations showing extraordinary ability dearomative methodology indicating their limitations future trends.
Язык: Английский
Процитировано
54
Nature Reviews Chemistry, Год журнала: 2024, Номер 8(8), С. 605 - 627
Опубликована: Июль 9, 2024
Язык: Английский
Процитировано
39
Journal of the American Chemical Society, Год журнала: 2022, Номер 144(38), С. 17680 - 17691
Опубликована: Сен. 15, 2022
Photochemical dearomative cycloaddition has emerged as a useful strategy to rapidly generate molecular complexity. Within this context, stereo- and regiocontrolled intermolecular para-cycloadditions are rare. Herein, method achieve photochemical of quinolines alkenes is shown. Emphasis placed on generating sterically congested products reaction highly substituted allenes. In addition, the mechanistic details process studied, which revealed reversible radical addition selectivity-determining recombination. The regio- stereochemical outcome also rationalized.
Язык: Английский
Процитировано
68
Chemical Science, Год журнала: 2023, Номер 14(43), С. 12004 - 12025
Опубликована: Янв. 1, 2023
Dearomative cycloaddition is a powerful technique to access sp
Язык: Английский
Процитировано
33
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)
Опубликована: Июль 3, 2023
Abstract The synthesis of polycyclic compounds is high interest due to the prevalence these motifs in drugs and natural products. Herein, we report on stereoselective construction 3D bicyclic scaffolds azetidine derivatives by modulation N ‐sulfonylimines achieve either [4+2]‐ or [2+2]‐cycloaddition reactions. utility method was established further product. Mechanistic studies are also included, which support reaction via Dexter energy transfer.
Язык: Английский
Процитировано
25
Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6600 - 6624
Опубликована: Янв. 1, 2024
Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.
Язык: Английский
Процитировано
13