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

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Ноя. 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.

Язык: 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

и другие.

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1854 - 1941

Опубликована: Янв. 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

Язык: Английский

Процитировано

5
Radical Brook rearrangement: past, present, and future DOI
Yunxiao Zhang, Gang Zhou, Shanshan Liu

и другие.

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

5
Photosensitized Imino-Thiocyanation of Alkenes DOI
Cong Huang, Zhenzhen Xie, Jie Gao

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

Процитировано

3
Development of a Phototriggered Diradical Phosphoamination Strategy of Alkenes DOI

Apurba Samanta,

Partha Pratim Mondal,

Goutam Bej

и другие.

Organic Letters, Год журнала: 2025, Номер 27(2), С. 606 - 611

Опубликована: Янв. 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.

Язык: Английский

Процитировано

1
Paired Electro‐Synthesis of Remote Amino Alcohols with/in H2O DOI Open Access
Zhixiong Ruan,

Xinyue Fang,

Xinwei Hu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 13, 2024

Abstract Amino alcohols, particularly remote amino alcohols and peptide are valuable due to their functional diversity in biologically active compounds. However, traditional synthesis methods face significant challenges, making electrochemistry an attractive alternative. We have developed a mild biocompatible sequential paired electrolysis strategy, leveraging copper‐electrocatalysis synthesize diverse including unnatural alcohols. Both experimental results density theory (DFT) calculations demonstrated that water serves as both the hydroxyl source solvent, facilitating generation of CuH with Cu(I) at cathode, which turn reduces aldehyde intermediates formed during reaction.

Язык: Английский

Процитировано

5
Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins DOI

Hao‐Cong Li,

Ming Zhang, Qi‐Yan Lv

и другие.

Chinese Chemical Letters, Год журнала: 2024, Номер unknown, С. 110579 - 110579

Опубликована: Окт. 1, 2024

Язык: Английский

Процитировано

4
Synthesis of β-Silyl Amines via Merging Photoinduced Energy and Hydrogen Atom Transfer in Flow DOI
Yu Shao,

Cheng-jie Ying,

Yuan-Cui Wan

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

The development of efficient methods for synthesizing β-silyl amines has long been a significant goal in organic synthesis. Previous mainly relied on the use prefunctionalized substrates or special reagents. Herein, we present visible-light-promoted synthesis approach amines, utilizing combination photoinduced energy and hydrogen atom transfer processes. Using flow chemistry technology, variety valuable skeletons, including α-amino esters, can be produced from readily available feedstocks such as hydrosilanes simple alkanes. Moreover, strategy's full-process fluidized production capability highlights its potential industrial-scale manufacturing. Mechanistic studies revealed that oxime esters act radical precursors well

Язык: Английский

Процитировано

3
Photocatalytic Synthesis of β-Amino Acid Derivatives from Alkenes with Alkyl Formates DOI

Cheng-jie Ying,

Yu Shao, Yi Wan

и другие.

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The synthesis of β-amino acid esters was achieved through the combination three-components radical coupling, hydrogen atom transfer and energy processes, utilizing alkyl formates olefins as raw materials in a light-induced reaction.

Язык: Английский

Процитировано

3
Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling DOI Creative Commons
Guohui Zeng,

Dongwen Guo,

Huanfeng Jiang

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

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

и другие.

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

Процитировано

0