Visible-Light Induced and Iron Peroxo-Promoted Radical Difunctionalization of Alkene for the Synthesis of β-Ketosulfone and α-Chloroketone DOI
Xinyu Zhu, Chen Bao, Xingxian Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 26, 2024

In this work, a switchable synthesis of β-ketosulfone and α-chloroketone through radical difunctionalization alkenes is reported. The transformation works well under iron peroxo species/photoredox dual catalysis an open-flask atmosphere, the reaction highlighted with good yields broad scope. Mechanism studies show that initiated by formal [4 + 2] cyclization sulfonyl in regioselective manner.

Language: Английский

Defluorinative Cyclization of Enamides with Fluoroalkyl Halides Through Two Vicinal C(sp3)─F Bonds Functionalization DOI Creative Commons

Yu‐Lan Chen,

Wei Han,

Yuanyuan Ren

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

Abstract Introducing distinctive functional groups to expand the structural diversity and improve intrinsic properties of parent molecules has been an essential pursuit in organic chemistry. By using perfluoroalkyl halide (PFAH) as a nontraditional, readily available, ideal 1,2‐difluoroalkenyl coupling partner, defluorinative cyclization reaction enamides for construction fluoroalkenyl oxazoles is first developed. The selective controllable two‐fold cleavage vicinal C(sp 3 )─F bonds PFAH not only enables introduction specific moiety with ease but also results functionalization two 2 )─H without need metal catalyst, photocatalyst, oxidant, or light. method can be applied late‐stage modification complex molecules, synthesis biological‐relevant oxazole analoges, scale‐up synthesis, which all further highlight real‐world utility this protocol. Mechanistic studies reveal that possibly proceeds through radical perfluoroalkylation, consecutive C─F bond heterolytic cleavage, process. In addition, situ formed may serve hydrogen abstractor.

Language: Английский

Citations

9

Fluoroalkylative Ketonization of Malononitrile-Tethered Alkenes via Nickel Electron-Shuttle and Lewis Acid Catalysis DOI

Yangkun Zhou,

Hanmin Huang

Organic Letters, Journal Year: 2024, Volume and Issue: 26(21), P. 4532 - 4536

Published: May 21, 2024

A binary Ni/Eu catalytic system has been developed, which enables an efficient reductive dicarbofunctionalization of unactivated alkenes with alkyl halides and malononitriles. The combination Ni electron-shuttle catalysis Eu(OTf)

Language: Английский

Citations

4

Dialkylation of CF2 unit enabled by cobalt electron-shuttle catalysis DOI Creative Commons
Changqing Rao, Tianze Zhang, Hanmin Huang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 10, 2024

Language: Английский

Citations

4

Generation of perthiyl radicals for the synthesis of unsymmetric disulfides DOI Creative Commons

Fei Zhou,

X. He, Mi Zhou

et al.

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

Published: Jan. 2, 2025

Unsymmetric disulfides are prevalent in natural products and essential medicinal chemistry materials science, but their robust synthesis poses significant challenges. In this paper, we report an expeditous transition-metal-free methodology for synthesizing unsymmetric through the addition of perthiyl radicals to alkenes. This study marks use generating by reacting SO2 with unactivated alkyl (pseudo)halides (Cl/Br/I/OTs). Various primary, secondary tertiary substituted different functional groups successfully function as suitable reactants. The formation involvement reaction process verified mechanistic studies DFT calculations. Overall, method leverages readily available electrophiles alkenes alongside a single setup efficiently form both carbon-sulfur sulfur-sulfur bonds simultaneously. Here, authors novel transition-metalfree

Language: Английский

Citations

0

Radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes to access vinyl and alkyl sulfones DOI
Jinhui Liu,

Fang Long,

Qing Li

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A radical-mediated sulfonylation relay of alkyl alkynes/alkenes with electron-deficient alkenes using Na 2 S O 4 as a linker is developed to synthesize highly selective ( Z )-vinyl and sulfones under metal-free catalyzed system.

Language: Английский

Citations

0

Dialkylation of Alkenes to Fluorinated δ-Lactams Enabled by Nickel-Electron-Shuttle Catalysis DOI

Sunfeng Ye,

Bangkui Yu, Hanmin Huang

et al.

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

Published: March 24, 2025

The δ-lactam motif is a privileged pharmacophore in drug design and development. While these biologically relevant molecules could be assembled through two-component cyclization, modular approach to constructing structures via multicomponent reaction with unactivated alkenes as starting materials rare. Herein, we report tandem that integrates alkene-dialkylation radical-involved ring-opening cyclization under single metal-electron-shuttle catalysis, which represents the most expeditious access fluorinated δ-lactams from simple alkenes.

Language: Английский

Citations

0

Transition-Metal-Catalyzed Regiodivergent Sulfonylation of Aziridrines for the Synthesis of β‑Amino Sulfones DOI

Qinqiong Zeng,

Yujia Gong,

X. He

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(22), P. 6340 - 6346

Published: Jan. 1, 2024

We developed the first transition-metal-catalyzed, regiodivergent sulfonylation of aziridines, enabling efficient synthesis diverse β-amino sulfones under mild conditions with broad substrate compatibility and high regioselectivity.

Language: Английский

Citations

3

A Noncationic Biocatalytic Nanobiohybrid Platform for Cytosolic Protein Delivery Through Controlled Perturbation of Intracellular Redox Homeostasis DOI Creative Commons

Wanyue Lu,

Weidong Wang,

Yimin Gong

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 16, 2024

Abstract Intracellular delivery of proteins has largely been relying on cationic nanoparticles to induce efficient endosome escape, which, however, poses serious concerns the inflammatory and cytotoxic effects. Herein, a versatile noncationic nano biohybrid platform is introduced for cytosolic protein by utilizing nano‐confined biocatalytic reaction. This constructed co‐immobilizing glucose oxidase (GOx) target into nanoscale hydrogen‐bonded organic frameworks (HOFs). The reaction GOx leveraged controlled perturbation intracellular redox homeostasis sustained hydrogen peroxide (H 2 O ) production diminishing flux pentose phosphate pathway (PPP). in turn induces escape nanobiohybrids. Concomitantly, GOx‐mediated hypoxia leads overexpression azo reductase that initiated materials' self‐destruction releasing proteins. These biological effects collectively highly delivery. versatility this further demonstrated various types proteins, different loading approaches (in situ immobilization or post‐adsorption), multiple cell lines. Finally, efficiency biosafety are tumor‐bearing mouse model. nanohybrid system opens up new avenues expected be extensively applicable broad range biomolecuels.

Language: Английский

Citations

2

Electron-shuttle catalysis enables regioselective and stereospecific dialkylation of alkynes DOI
Zhiting Wang,

Changqing Rao,

Hanmin Huang

et al.

Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101129 - 101129

Published: Oct. 1, 2024

Language: Английский

Citations

2

Advances in the Synthesis of Sulfur-Containing Cyclic Architectures via Insertion of SO2 DOI
Chao Shu,

Xi Lu,

Yuyang Huang

et al.

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: April 6, 2024

Abstract Sulfur-containing heterocycles, where the S(R) moiety is located within cyclic structure, have found tremendous applications in fields of chemical, pharmaceutical, and materials sciences due to their unique biological pharmaceutical activities. Recent years witnessed increasing interest sulfur-containing new methods for synthesis been reported by adopting modern methodologies technologies through insertion sulfur dioxide. The main objective this Account overview latest major developments on heterocyclic systems, mainly covering thermo-, photo- electron-induced cyclization dioxide (SO2). We aim provide readership with a comprehensive understanding topic offer positive outlook promising future field. 1 Introduction 2 Thermal-Induced Cyclization 3 Photoinduced Radical 4 Electron-Induced 5 Conclusion

Language: Английский

Citations

1