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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Photoinduced, additive- and photosensitizer-free multi-component synthesis of naphthoselenazol-2-amines with air in water

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 7983 - 7987

Published: Jan. 1, 2023

An atom- and step-economical, efficient eco-friendly method for constructing naphthoselenazol-2-amines through a visible-light photocatalytic multi-component reaction under aqueous phase conditions is reported.

Language: Английский

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Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7214 - 7261

Published: May 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Language: Английский

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Recent advances in combining photo- and N-heterocyclic carbene catalysis

Chemical Science, Journal Year: 2023, Volume and Issue: 14(46), P. 13367 - 13383

Published: Jan. 1, 2023

This review summarizes recent advances in combining photo- and N-heterocyclic carbene catalysis, as well provides an outlook on future opportunities challenges.

Language: Английский

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General and Modular Route to (Halo)alkyl BCP-Heteroaryls Enabled by α-Aminoalkyl Radical-Mediated Halogen-Atom Transfer

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(2), P. 619 - 627

Published: Dec. 28, 2023

Synthesis of bicyclo[1.1.1]pentane (BCP) heteroaryls continues to be a part the most important tasks in organic synthesis because they are significant class bioisosteres with universal applications drug discovery. However, substrate scope current multicomponent reactions is limited tertiary alkyl radicals and prefunctionalized (het)arenes due their intrinsic mechanisms, resulting decrease application value. Herein, we report straightforward alternative for (halo)alkyl BCP-heteroaryls from [1.1.1]propellane enabled by α-aminoalkyl radical-mediated halogen-atom transfer (XAT). Carbon derived commonly available precursors such as primary, secondary, halides polyhalides perform additions onto give BCP radicals, which then engage C–H/C–C couplings different heteroarenes. A wide range easily constructed moderate-to-good yields. Late-stage functionalization performed on approved derivatives proceeds good efficiency produce corresponding BCP-heteroaryls. The control experiments density functional theory (DFT) calculations reveal radical nature reaction. This approach not only verifies (XAT) strategy but also provides practical efficient route multifunctionalized BCPs, significantly expands BCP-heteroaryl-type development.

Language: Английский

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Light‐Driven Synthesis and Functionalization of Bicycloalkanes, Cubanes and Related Bioisosteres

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Jan. 5, 2024

Bicycloalkanes, cubanes and their structural analogues have emerged as bioisosteres of (hetero)arenes. To meet increasing demand, the chemical community has developed a plethora novel synthetic methods. In this review, we assess progress made in field light-driven construction functionalization such relevant molecules. We focused on diverse targets, well reaction processes giving access to: (i) [1.1.1]-bicyclopentanes (BCPs); (ii) [2.2.1]-bicyclohexanes (BCHs); (iii) [3.1.1]-bicycloheptanes (BCHeps); (iv) cubanes; other structurally related scaffolds. Finally, future perspectives dealing with identification manifolds to new functionalized bioisosteric units are discussed.

Language: Английский

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Photoinduced C(sp³)−H Bicyclopentylation Enabled by an Electron Donor–Acceptor Complex‐Mediated Chemoselective Three‐Component Radical Relay

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: April 10, 2024

The photoredox electron donor-acceptor (EDA) complex-mediated radical coupling reaction has gained prominence in the field of organic synthesis, finding widespread application two-component reactions. However, EDA complex-promoted multi-component reactions are not well developed with only a limited number examples have been reported. Herein, we report photoinduced and highly chemoselective three-component arylalkylation [1.1.1]propellane, which allows direct functionalization C(sp

Language: Английский

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Photoredox/NHC cooperative catalysis for alkylacylation of styrenes: An alternative method for the synthesis of γ-aminoketones

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: 156, P. 155450 - 155450

Published: Jan. 8, 2025

Language: Английский

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Photocatalytic Three-Component Synthesis of 3-Heteroarylbicyclo[1.1.1]pentane-1-acetates

Organic Letters, Journal Year: 2023, Volume and Issue: 25(22), P. 4050 - 4055

Published: May 26, 2023

Herein, we report a visible-light-induced three-component reaction involving [1.1.1]propellane, diazoates, and various heterocycles for the synthesis of 3-heteroarylbicyclo[1.1.1]pentane-1-acetates. Throughout this reaction, radicals generated from diazoate species react with [1.1.1]propellane in an addition to form bicyclo[1.1.1]pentane (BCP) that subsequently heterocycles, leading formation 1,3-disubstituted BCP acetates. Notably, methodology exhibits excellent functional group compatibility, high atom economy, mild conditions, thus facilitating suitable synthetic access

Language: Английский

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Photocatalyzed 1,3-Bromodifluoroallylation of [1.1.1]Propellane with α-Trifluoromethylalkenes and KBr Salts

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6889 - 6893

Published: Aug. 6, 2024

Herein we unveil a visible-light-driven transition-metal-free 1,3-bromodifluoroallylation of [1.1.1]propellane. This reactivity is harnessed through organophotocatalysis, providing practical synthetic pathways to 1-brominated-3-

Language: Английский

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