Development of N-centered radical scavengers that enables photoredox-catalyzed transition-metal-free radical amination of alkyl pinacol boronates DOI Creative Commons
Changlei Zhu, Jiaxin Lin, Xiaoguang Bao

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 4, 2025

In recent years, amination of alkylboronates through ionic copper catalysis or boron-ate complex 1,2-metalation has been well established, but complementary radical processes remain less studied before. Herein, based on rational design, we develop several imine-type N-centered scavengers and apply them to the alkylboronates. The reaction proceeds under mild photoredox-catalyzed transition-metal-free conditions features excellent functional group tolerance. It also enables preparation a range medicinally valuable amine derivatives from natural products. Further application this reagent in C-H amination, deoxygenative decarboxylative three component trifluoromethylative/sulfonylative aminations are realized. mechanistic studies DFT calculations conducted provide detailed evidence for mechanism.

Language: Английский

Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors DOI
Qiao Sun, Shaopeng Wang, Yuan Xu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

Citations

1
Photoinduced Difunctionalization of Diazenes Enabled by N–N Radical Coupling DOI

Yu‐Shi Jiang,

Shanshan Li,

Xue-Ling Luo

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6671 - 6676

Published: Aug. 29, 2023

In this study, a metal-free difunctionalization strategy for diazenes was developed using range of bifunctionalization reagents. This involves unique N(sp3)–N(sp2) radical coupling between the hydrazine and imine radical. More than 30 triazane core motifs were constructed by installing imines various functional groups, including alkyl, phenyl, cyanoalkyl, sulfonyl on both ends nitrogen–nitrogen bond in an efficient manner.

Language: Английский

Citations

17
Photosensitized 1,2-Difunctionalization of Alkenes to Access β-Amino Sulfonamides DOI

Ze-Long Xiao,

Zhenzhen Xie,

Chu‐Ping Yuan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2108 - 2113

Published: March 5, 2024

A metal-free photosensitized 1,2-imino-sulfamoylation of olefins by employing a tailor-made sulfamoyl carbamate as the difunctionalization reagent has been established. This protocol exhibits versatility across broad substrate scope, including aryl and aliphatic alkenes, leading to synthesis diverse β-imino sulfonamides in moderate good yields. method is characterized its reaction system, mild conditions, excellent regioselectivity, high atom economy, serving promising platform for preparation β-amino sulfonamide-containing molecules, particularly context drug discovery.

Language: Английский

Citations

6
Carbamoylarylation of Alkenes with N-Aryl Oxamic Acids Involving 1,4-Aryl Migration Via C(aryl)–N Bond Cleavage DOI
Akira Shiozuka, Di Wu, Kyohei Kawashima

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5972 - 5977

Published: April 4, 2024

We report carbamoylarylation of alkenes using N-aryl oxamic acid derivatives under visible-light irradiation. Reactions with carbamoyl radicals generated to afford Giese-type products or 3,4-dihydroquinolin-2(1H)-ones via ortho-radical addition an aryl amide moiety have been previously reported. However, this study reveals that the introduction a removable bulky group onto nitrogen atom acids facilitates radical alkenes, resulting in 1,4-aryl migration C(aryl)–N bond cleavage, thus affording arylpropanamides. Various such as acrylic and styrene derivatives, are successfully applied synthesis variety arylpropanamide including 1,4-dicarbonyl amides, forming two C–C bonds.

Language: Английский

Citations

6
Three-Component Aminoheteroarylation of Alkenes via Photoinduced EDA Complex Activation DOI
Chengcheng Shi, Lin Guo, Han Gao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(42), P. 7661 - 7666

Published: Oct. 16, 2023

A catalyst-free approach for the multicomponent aminoheteroarylation reaction of alkenes with N-aminopyridinium salts and heteroarenes is herein described. The shows good functional group tolerance allows generation valuable β-heteroarylethylamines in satisfying yields. In this transformation, are utilized to generate electron donor–acceptor complexes, which undergo a single-electron transfer process upon light irradiation form key amidyl radicals heteroaryl radical cations. subsequently captured by alkenes, followed Minisci-type yield desired β-heteroarylamines as products.

Language: Английский

Citations

15
Photoinduced Direct Electron Transfer between Quinoxalin-2(1H)-ones and Alkyl Carboxylic Acids for C–H Alkylation DOI
Kaikai Niu,

Haoran Jiao,

Pan Zhou

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(50), P. 8970 - 8974

Published: Dec. 12, 2023

The progress of efficient and sustainable approaches for decarboxylative coupling reactions is synthetically appealing due to the structural diversity, lack toxicity, widespread commercial accessibility carboxylic acids. However, decarboxylation reaction still encounters challenges related utilization oxidants, catalysts, prefunctionalization conditions. We report herein a mild method that facilitates direct electron transfer between alkyl acids excited-state substrates C-H alkylation quinoxalin-2(1H)-ones without involvement any catalyst or additive.

Language: Английский

Citations

13
The Merger of Halogen Atom Transfer (XAT) and Energy Transfer Catalysis (EnT) for the Modular 1,2-Iminylalkylation of Diazenes DOI
Shanshan Li,

Yu‐Shi Jiang,

Li-Ning Chen

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(38), P. 7009 - 7013

Published: Sept. 14, 2023

The 1,2-iminylalkylation of diazenes using alkyl iodides in combination with an O-benzoyl oxime is reported. In this transformation, acted as a radical precursor and XAT mediator. addition to common iodides, other such iodomethane, iodomethane-d3, trifluoroiodomethane, ethyl difluoroiodoacetate, iodoalkanes containing unprotected hydroxyl amide groups can also serve C-radical precursors the electrophilic acceptors.

Language: Английский

Citations

12
Photoinduced Asymmetric Alkene Aminohetarylation with Chiral Sulfoximine Reagents DOI
Zhu Cao,

Sun Yu-qian,

Yasu Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 15, 2024

Abstract Given the pivotal role of β ‐(het)arylethylamine moiety in bioactive molecules, direct amino(het)arylation alkenes occupies a privileged position construction (het)arylethylamine derivatives. Herein we devise chiral sulfoximines as novel bifunctional reagents which exhibit remarkable efficiency challenging asymmetric alkene aminohetarylation reaction, particularly terms reactivity and stereo‐control. The can be conveniently accessed gram scale, efficiently generate N ‐centered radicals under mild photochemical conditions. transformation proceeds through enantioselective 1,4‐hetaryl migration, ensuring precise chirality transfer from sulfur‐ to carbon‐centers, rendering wide applicability both aromatic aliphatic alkenes. Furthermore, method is straightforward operate does not require transition metals or photosensitizers, making it an attractive practical option.

Language: Английский

Citations

4
Development of Fluorescent-Photothermal Probe Based on Photoinduced Energy Transfer: A Dual-Readout Immunosensor for the Detection of Illegal Additive DOI

Hongzhi Liang,

Aori Qileng, Haoran Shen

et al.

Biosensors and Bioelectronics, Journal Year: 2025, Volume and Issue: 273, P. 117140 - 117140

Published: Jan. 8, 2025

Language: Английский

Citations

0
Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling DOI Creative Commons
Guohui Zeng,

Dongwen Guo,

Huanfeng Jiang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.

Language: Английский

Citations

0