Organophotocatalytic [2+2] Cycloaddition of Electron‐Deficient Styrenes** DOI Creative Commons
Maxim Golfmann,

Louis Glagow,

Antonios Giakoumidakis

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(3)

Published: Oct. 25, 2022

A visible-light organophotocatalytic [2+2] cycloaddition of electron-deficient styrenes is described. Photocatalytic cycloadditions are typically performed with electron-rich styrene derivatives or α,β-unsaturated carbonyl compounds, and transition-metal-based catalysts. We have discovered that an organic cyanoarene photocatalyst able to deliver high-value cyclobutane products bearing aryl substituents in good yields. range tolerated, both homodimerisations intramolecular fused bicyclic systems available by using this methodology.

Language: Английский

Intermolecular [2π+2σ]-photocycloaddition enabled by triplet energy transfer DOI

Roman Kleinmans,

Tobias Pinkert,

Subhabrata Dutta

et al.

Nature, Journal Year: 2022, Volume and Issue: 605(7910), P. 477 - 482

Published: March 21, 2022

Language: Английский

Citations

262

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

Roman Kleinmans,

Constantin G. Daniliuc

et al.

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

Citations

128

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

48

Visible light-mediated intermolecular crossed [2+2] cycloadditions using a MOF-supported copper triplet photosensitizer DOI
Jun Guo, Qi Xia,

Wing Yi Tang

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(3), P. 307 - 320

Published: Feb. 23, 2024

Language: Английский

Citations

20

Energy- and atom-efficient chemical synthesis with endergonic photocatalysis DOI
Huaiju Wang, Ya‐Ming Tian,

Burkhard König

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(10), P. 745 - 755

Published: Sept. 23, 2022

Language: Английский

Citations

64

High Triplet Energy Iridium(III) Isocyanoborato Complex for Photochemical Upconversion, Photoredox and Energy Transfer Catalysis DOI Creative Commons
Lucius Schmid, Felix Glaser,

Raoul S. Schaer

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(2), P. 963 - 976

Published: Jan. 5, 2022

Cyclometalated Ir(III) complexes are often chosen as catalysts for challenging photoredox and triplet-triplet-energy-transfer (TTET) catalyzed reactions, they of interest upconversion into the ultraviolet spectral range. However, triplet energies commonly employed photosensitizers typically limited to values around 2.5-2.75 eV. Here, we report on a new luminophore, with an unusually high energy near 3.0 eV owing modification previously reported complex isocyanoborato ligands. Compared nonborylated cyanido precursor complex, introduction B(C6F5)3 units in second coordination sphere results substantially improved photophysical properties, particular luminescence quantum yield (0.87) long excited-state lifetime (13.0 μs), addition energy. These favorable properties (including good long-term photostability) facilitate exceptionally organic photoreactions (sensitized) triplet-triplet annihilation fluorescent singlet excited state beyond 4 eV, deep region. The photocatalyzes sigmatropic shift [2 + 2] cycloaddition reactions that unattainable common transition metal-based photosensitizers. In presence sacrificial electron donor, it furthermore is applicable demanding photoreductions, including dehalogenations, detosylations, degradation lignin model substrate. Our study demonstrates how rational ligand design transition-metal underexplored effects) can be used enhance their thereby broaden application potential solar conversion synthetic photochemistry.

Language: Английский

Citations

62

The Impact of Boron Hybridisation on Photocatalytic Processes DOI Creative Commons

Alessandro Marotta,

Callum E. Adams,

John J. Molloy

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: June 24, 2022

Recently the fruitful merger of organoboron chemistry and photocatalysis has come to forefront organic synthesis, resulting in development new technologies access complex (non)borylated frameworks. Central success this combination is control boron hybridisation. Contingent on photoactivation mode, as its neutral planar form or tetrahedral boronate can be used regulate reactivity. This Minireview highlights current state art photocatalytic processes utilising compounds, paying particular attention role hybridisation for target transformation.

Language: Английский

Citations

56

Photosensitized [2+2]‐Cycloadditions of Alkenylboronates and Alkenes DOI
Yanyao Liu, Dongshun Ni,

Bernard G. Stevenson

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 21, 2022

A new strategy for the synthesis of highly versatile cyclobutylboronates via photosensitized [2+2]-cycloaddition alkenylboronates and alkenes is presented. The process mechanistically different from other processes in that energy transfer occurs with alkenylboronate as opposed to alkene. This allows an array diverse cyclobutylboronates. conversion these adducts compounds well their utility melicodenine C demonstrated.

Language: Английский

Citations

42

Visible Light Photoredox-Catalyzed Decarboxylative Alkylation of 3-Aryl-Oxetanes and Azetidines via Benzylic Tertiary Radicals and Implications of Benzylic Radical Stability DOI Creative Commons
Maryne A. J. Dubois, Juan J. Rojas, Alistair J. Sterling

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(10), P. 6476 - 6488

Published: March 3, 2023

Four-membered heterocycles offer exciting potential as small polar motifs in medicinal chemistry but require further methods for incorporation. Photoredox catalysis is a powerful method the mild generation of alkyl radicals C–C bond formation. The effect ring strain on radical reactivity not well understood, with no studies that address this question systematically. Examples reactions involve benzylic are rare, and their challenging to harness. This work develops functionalization oxetanes azetidines using visible light photoredox prepare 3-aryl-3-alkyl substituted derivatives assesses influence heterosubstitution small-ring radicals. 3-Aryl-3-carboxylic acid suitable precursors tertiary oxetane/azetidine which undergo conjugate addition into activated alkenes. We compare oxetane other systems. Computational indicate Giese additions unstrained acrylates reversible result low yields dimerization. Benzylic part strained ring, however, less stable more π-delocalized, decreasing dimer increasing product Oxetanes show high due Bent's rule rendering irreversible.

Language: Английский

Citations

26

Palladium-catalyzed selective alkoxycarbonylation of different alcohols toward the direct synthesis of cyclobutanecarboxylates DOI
Yukun Liu,

Xing‐Wei Gu,

Yanhua Zhao

et al.

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115956 - 115956

Published: Jan. 1, 2025

Language: Английский

Citations

2