Visible light-induced chemoselective 1,2-diheteroarylation of alkenes DOI Creative Commons

Shiyu Guo,

Yi-Peng Liu, Jingsong Huang

et al.

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

Published: July 19, 2024

Abstract Visible-light photocatalysis has evolved as a powerful technique to enable controllable radical reactions. Exploring unique photocatalytic mode for obtaining new chemoselectivity and product diversity is of great significance. Herein, we present photo-induced chemoselective 1,2-diheteroarylation unactivated alkenes utilizing halopyridines quinolines. The ring-fused azaarenes serve not only substrate, but also potential precursors halogen-atom abstraction pyridyl generation in this photocatalysis. As complement metal catalysis, process with mild redox neutral conditions assembles two different heteroaryl groups into regioselectively contribute broad substrates scope. obtained products containing aza-arene units permit various further diversifications, demonstrating the synthetic utility protocol. We anticipate that protocol will trigger advancement alkyl/aryl halides activation.

Language: Английский

Energy transfer photocatalysis: exciting modes of reactivity DOI
Subhabrata Dutta, Johannes E. Erchinger, Felix Strieth‐Kalthoff

et al.

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

Citations

136
ortho-Selective Dearomative [2π + 2σ] Photocycloadditions of Bicyclic Aza-Arenes DOI

Roman Kleinmans,

Subhabrata Dutta,

Kristers Ozols

et al.

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

Citations

121
Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols DOI
Subhabrata Dutta, Donghyeon Lee,

Kristers Ozols

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2789 - 2797

Published: Jan. 18, 2024

Dearomative photocycloaddition of monocyclic arenes is an appealing strategy for comprehending the concept "escape from flatland". This brings replacement readily available planar aromatic hydrocarbon units with a 3D fused bicyclic core sp3-enriched carbon units. Herein, we outline intermolecular approach dearomative phenols. In order to circumvent ground-state aromaticity and construct conformationally restrained building blocks, bicyclo[1.1.0]butanes were chosen as coupling partners. renders straightforward access bicyclo[2.1.1]hexane unit cyclic enone moiety, which further contributed synthetic linchpin postmodifications. Mechanistic experiment advocates plausible onset both reactants, depending on redox potential.

Language: Английский

Citations

62
Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines DOI Creative Commons
Marcos Escolano, Daniel Gaviña, G. Alzuet

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(3), P. 1122 - 1246

Published: Jan. 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.

Language: Английский

Citations

54
Energy-transfer-induced [3+2] cycloadditions of N–N pyridinium ylides DOI
Wooseok Lee, Yejin Koo, Hoimin Jung

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(8), P. 1091 - 1099

Published: June 26, 2023

Language: Английский

Citations

46
Three-dimensional saturated C(sp3)-rich bioisosteres for benzene DOI
Jet Tsien, Chao Hu, Rohan R. Merchant

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(8), P. 605 - 627

Published: July 9, 2024

Language: Английский

Citations

39
Rejuvenation of dearomative cycloaddition reactions via visible light energy transfer catalysis DOI Creative Commons

Angshuman Palai,

Pramod Rai,

Biplab Maji

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(43), P. 12004 - 12025

Published: Jan. 1, 2023

Dearomative cycloaddition is a powerful technique to access sp

Language: Английский

Citations

33
Advances and Prospects in Understanding London Dispersion Interactions in Molecular Chemistry DOI Creative Commons
Lars Rummel, Peter R. Schreiner

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(12)

Published: Dec. 5, 2023

London dispersion (LD) interactions are the main contribution of attractive part van der Waals potential. Even though LD effects driving force for molecular aggregation and recognition, role these omnipresent in structure reactivity had been largely underappreciated over decades. However, recent years considerable efforts have made to thoroughly study their potential as a chemical design element structures catalysis. This was possible through fruitful interplay theory experiment. review highlights results advances utilizing structural motif understand utilize intra- intermolecularly LD-stabilized systems. Additionally, we focus on quantification fundamental reactions.

Language: Английский

Citations

30
Photosensitized [4+2]‐ and [2+2]‐Cycloaddition Reactions of N‐Sulfonylimines DOI Creative Commons

Wang Wang,

M. Kevin Brown

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: July 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.

Language: Английский

Citations

25
Photochemical dearomative skeletal modifications of heteroaromatics DOI Creative Commons
Peng Ji, Kuaikuai Duan, Menglong Li

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(12), P. 6600 - 6624

Published: Jan. 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.

Language: Английский

Citations

13