Asymmetric synthesis of β-amino acid derivatives by stereocontrolled C(sp3)-C(sp2) cross-electrophile coupling via radical 1,2-nitrogen migration DOI Creative Commons
Shi Tang,

Zi-Cheng Liao,

Mengwu Xiao

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Abstract Optically pure non-natural β-amino acids are noteworthy molecular motifs of numerous pharmaceutically important molecules. Skeletal editing abundant α-amino acid scaffolds via tandem radical 1,2-N-shift/cross-coupling represents an attractive and powerful tool to straightforward assemble new molecules; however, this strategy presents substantial challenges owing difficulties in reactivity regio-/enantiocontrol. Herein, we report unprecedented remote cross-electrophile C(sp2)-C(sp3) coupling β-bromo esters with aryl bromides a π-system-independent 1,2-N-shift, which allows access α-arylated β-amino high efficiency regioselectivity. Furthermore, upon the novel cooperative catalysis Ni(II)/new-style Box complex chiral phosphoric (CPA), migratory further achieves enantioselectivity control C(sp3)–C(sp2) bond construction. In addition, detailed experimental studies DFT calculations were conducted gain insight into mechanism origin enantioselectivity, was evidenced by two-step synthesis pan-Akt inhibitor molecule. Overall, synergistic expands these methods challenging enantioselective C(sp2)–C(sp3) 1,2-amino migration.

Language: Английский

Radical Brook rearrangement: past, present, and future DOI
Yunxiao Zhang, Gang Zhou, Shanshan Liu

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review aims to provide an overview of radical Brook rearrangement, which is organized by grouping three type reactive species generated via the unique rearrangement process.

Language: Английский

Citations

4
Photosensitized Imino-Thiocyanation of Alkenes DOI
Cong Huang, Zhenzhen Xie, Jie Gao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

A metal-free photosensitized 1,2-imino-thiocyanation of olefins has been established by using the easily accessible bifunctional reagent S-cyano-N-(diphenylmethylene) thiohydroxylamine. wide range were successfully transformed into corresponding β-iminothiocyanates in moderate to high yields. This protocol stands out for its nature, broad substrate compatibility, and atom step economy, providing an effective strategy assembling β-amino thiocyanate-containing scaffolds.

Language: Английский

Citations

3
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

2
Development of a Phototriggered Diradical Phosphoamination Strategy of Alkenes DOI

Apurba Samanta,

Partha Pratim Mondal,

Goutam Bej

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(2), P. 606 - 611

Published: Jan. 6, 2025

Aminophosphonates serve as extremely important moieties with respect to their activities in biological systems. However, incorporating a Nitrogen and Phosphorus moiety by conventional techniques ionic mode is usually associated extensive prefunctionalization of the substrates, employing harsh conditions reagents that limit viability these methods. Introducing both components radicals may be viable option. We hereby propose an overhaul existing reactivity paradigm demonstrating photocatalytic diradical-based approach, where new iminophosphonating are rationally designed developed used extensively homolytic cleavage for simultaneously installing iminyl phosphonyl groups onto alkenes.

Language: Английский

Citations

1
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
Enhanced Photoredox Activity in Nitrogen‐Doped Carbon Nitride for Heterogeneous Nitrogen and Oxygen Radical Reactions DOI Creative Commons
Lan Qin, Huan Liu, Wei Yi

et al.

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

Published: Feb. 22, 2025

Abstract A nitrogen‐doped carbon nitride (NCN) has been synthesized and utilized for the sustainable generation of reactive nitrogen oxygen radicals under mild photocatalytic conditions. This material exhibits a significant improvement in separation transfer photoexcited charge carriers, which facilitates direct activation N─H O─H bonds to achieve variety radical carboamination, oxyamination deoxygenation reactions. The NCN catalyst further demonstrated its robust photoredox activity through several successful applications, including aerobic oxidation boronic acids controllable alcohols aldehydes carboxylic acids. Moreover, maintains reactivity efficiency even after multiple cycles use, showcasing durability potential practical applications chemistry.

Language: Английский

Citations

0
Paired Electrolysis Enabled Remote Amino Alcohols Synthesis DOI
Haonan Zhang, Kun Xu

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 722 - 722

Published: Jan. 1, 2025

Language: Английский

Citations

0
Facile, efficient and green phthalimide synthesis in supercritical carbon dioxide DOI
Vadim Filatov, Dmitrii A. Iuzabchuk, Dmitry A. Guk

et al.

Mendeleev Communications, Journal Year: 2025, Volume and Issue: 35(3), P. 341 - 343

Published: Jan. 1, 2025

Language: Английский

Citations

0
Light-Driven Synthesis of 2-Aminoethanol from Formaldehyde and Ammonia DOI
Shihao Li, Jiafu Shi, Yu Chen

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6595 - 6605

Published: April 8, 2025

Language: Английский

Citations

0
Photocatalytic Iminothiolation of Alkenes via Monothiocarbonate Oxime Esters DOI
Ranjini Laskar,

Rebecca E. Thielemann,

Janosch Knüppe

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6731 - 6738

Published: April 10, 2025

Language: Английский

Citations

0