Asymmetric Amination of Unstrained C(sp3)–C(sp3) Bonds DOI Creative Commons
Yang Liu,

Ye‐Wei Chen,

Yuanxiang Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29857 - 29864

Published: Oct. 16, 2024

The asymmetric functionalization of unstrained C(sp3)–C(sp3) bonds could be a powerful strategy to stereoselectively reconstruct the backbone an organic compound, but such reactions are rare. Although allylic substitutions have been used frequently construct C–C by cleavage more reactive C–X (X is usually O atom ester) transition metals, reverse process that involves replacement bond with C–heteroatom rare and generally considered thermodynamically unfavorable. We show unstrained, inert σ can converted C–N via designed solubility-control strategy, which makes unfavorable possible. amination occurs range amine nucleophiles cleaves multiple classes alkyl in good yields high enantioselectivity. A novel resolution also reported transforms racemic amines corresponding optically active sequential conversion back bond. Mechanistic studies formation rate-limiting step driven low solubility salt formed from cleaved group nonpolar solvent.

Language: Английский

Nitrogenative Degradation of Polystyrene Waste DOI

Ganfei Zeng,

Yanming Su,

Jianwei Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Owing to massive production and poor end-of-life management, plastic waste pollution has become one of the most pressing environmental crises. In response mounting crisis, past several decades have witnessed development numerous methods technologies for recycling. However, current recycling often produce low-quality or low-value products, making it difficult recover operating costs. To this end, we report a novel preoxygenation-induced strategy nitrogenative degradation real-life polystyrene plastics into high-value aromatic nitrogen compounds in cost-effective manner. Thus, expensive highly demanding benzonitrile as well benzamide were obtained up 74% overall isolated yield from by using CuBr catalyst, O2 oxidant, CH3CN source. Detailed mechanistic investigations indicate that hydroxyl radicals activation play role selective aerobic process. Furthermore, multiple reaction pathways contribute formation benzamide.

Language: Английский

Citations

3
Carbon-carbon triple bond cleavage and reconstitution to achieve aryl amidation using nitrous acid esters DOI Creative Commons
Ziying Wang, Shoujun Wang,

Nan‐Nan Dai

et al.

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

Published: Jan. 24, 2025

C–C bond cleavage and recombination provide an efficient strategy for the modification reconstruction of molecule structures. Herein, we present a method achieving amidation aryl C(sp2)–H through triple with involvement nitrous acid esters. This marks instance precise controlled stepwise bond, offering fresh perspective such bonds. Nitrous ester serves as both radical source hydrogen atom transfer (HAT) reagent to functionalize utilize two carbon atoms bond. The alkoxy captures from or N-hydroxyl induce 1,3-oxygen migration, which is crucial subsequent molecular authors report achieve bonds by participation

Language: Английский

Citations

3
Photochemical reactions as synthetic tool for pharmaceutical industries DOI
Shehla Khalid, Muhammad Bılal, Nasır Rasool

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(9), P. 109498 - 109498

Published: Jan. 6, 2024

Language: Английский

Citations

9
Deacylative Homolysis of Ketone C(sp3)–C(sp2) Bonds: Streamlining Natural Product Transformations DOI
Michal Šimek, Sujit Mahato,

Brady W. Dehnert

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The homolytic cleavage of C–C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility ketones, radical fragmentation their α-C–C proven be formidable challenge. Here, we present broadly applicable deacylative strategy designed homolytically cleave aliphatic ketones various complexities, including transformations cycloalkanones into carboxylic acids tethered C-centered free radicals that can engaged in diverse radical-based processes. method involves ketone activation through treatment with hydrogen peroxide, yielding gem-dihydroperoxides. Subsequent single-electron-transfer reduction mediated by low-valent metal complex generates alkyl captured selectively radicophile choice, catalytic cross-coupling. logic our functionalization is exemplified total synthesis 14 natural products, one analogue, two drugs starting from readily available showcasing its transformative power settings. This obviates need reagents allows controlled conversion reconstructed making process highly across spectrum domains.

Language: Английский

Citations

1
Recent Advances and Developments in Solar-driven photothermal catalytic CO2 reduction into C2+ products DOI Creative Commons

Xiuting Wu,

Senlin Zhang, Shangbo Ning

et al.

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

Published: Jan. 1, 2025

Solar-driven catalytic conversion of carbon dioxide (CO2) into value-added C2+ chemicals and fuels has attracted significant attention over the past decades, propelled by urgent environmental energy demands. However, reduction CO2 continues to face challenges due inherently slow kinetics. This review traces historical development current state photothermal reduction, detailing mechanisms which is transformed products. A key focus on catalyst design, emphasizing surface defect engineering, bifunctional active site co-catalyst coupling enhance efficiency selectivity solar-driven synthesis. Key reaction pathways both C1 products are discussed, ranging from CO, CH4 methanol (CH3OH) synthesis production C2-4 such as hydrocarbons, ethanol, acetic acid, various carbonates. Notably, advanced C5+ hydrocarbons exemplifies remarkable potential technologies effectively upgrade CO2-derived products, thereby delivering sustainable liquid fuels. provides a comprehensive overview fundamental mechanisms, recent breakthroughs, pathway optimizations, culminating in valuable insights for future research industrial-scale prospect reduction.

Language: Английский

Citations

1
Three-Component Synthesis of Multiple Functionalized Allenes via Copper/Photoredox Dual Catalyzed 1,4-Alkylcyanation of 1,3-Enynes DOI

Yue Pu,

Shumin Ding, Hai‐Xia Zhao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1834 - 1839

Published: Feb. 22, 2024

Efficient access to multiple functionalized allenes via a three component 1,4-alkylcyanation of enynes with cyclic alcohol derivatives in the presence trimethylsilyl cyanide (TMSCN) under copper/photoredox dual catalysis has been developed. Both easily transformable aldehyde and cyano groups were introduced tetra-substituted through light-induced C–C bond cleavage butanol pentanol derivatives. The reactions proceeded smoothly mild conditions broad functional tolerance.

Language: Английский

Citations

7
Electrochemical Formation of Oxazolines by 1,3-Oxyfluorination of Non-activated Cyclopropanes DOI

Madara Da̅rziņa,

Aigars Jirgensons

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2158 - 2162

Published: March 8, 2024

The C–C bond in non-activated cyclopropanes can be intramolecularly cleaved with an electrochemically generated amidyl radical forming oxazolines. In the presence of TBABF4, this provides 1,3-oxyfluorination products. cleavage cyclopropane proceeds inversion configuration, suggesting intramolecular homolytic substitution (SHi) mechanism. performance TBABF4 as efficient fluoride source was explained by accumulation BF4– anion at anode surface, which a carbocation is formed oxidation C-centered radical.

Language: Английский

Citations

5
Selective nitrogen insertion into aryl alkanes DOI Creative Commons

Zheng Zhang,

Decheng Li, Zengrui Cheng

et al.

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

Published: July 17, 2024

Abstract Molecular structure-editing through nitrogen insertion offers more efficient and ingenious pathways for the synthesis of nitrogen-containing compounds, which could benefit development synthetic chemistry, pharmaceutical research, materials science. Substituted amines, especially alkyl heterocyclic are widely found in nature products drugs. Generally, accessing these compounds requires multiple steps, result low efficiency. In this work, a molecular editing strategy is used to realize using aryl alkanes as starting materials. Using derivatives O -tosylhydroxylamine source, method enables precise into C sp 2 -C 3 bond alkanes. Notably, further applications demonstrate that be prepare bioactive molecules with good efficiency modify skeleton Furthermore, plausible reaction mechanism involving transformation carbocation imine intermediates has been proposed based on results control experiments.

Language: Английский

Citations

5
Versatile deacylative cross-coupling of aromatic ketones DOI Creative Commons
Hikaru Nakahara, Ryota Isshiki, Masayuki Kubo

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(9), P. 2916 - 2930

Published: July 29, 2024

Transition metal-catalyzed cross-couplings represent the most dependable techniques for linking aryl electrophiles with nucleophiles to synthesize a diverse array of valuable aromatic compounds. Although ketones are crucial intermediates in synthesis compounds numerous known methods carbonyl transformations and ring modifications, few consider them as suitable cross-coupling. This is primarily because forming new bonds requires cleavage strong C–C bond. Herein, we introduce cross-coupling method that effectively utilizes versatile electrophiles. The cornerstone our strategy transformation into esters via sequential Claisen regioselective retro-Claisen condensations. resulting then capable undergoing reactions various one-pot process.

Language: Английский

Citations

4
Mechanistic Insights into CYP199A4-Catalyzed α-Hydroxyketone Formation and Hydrogen Bond-Assisted C–C Bond Cleavage Catalyzed by the CYP199A4 F182L Mutant DOI Open Access
Chang Yuan, Jiaqi Xu, Shun Wang

et al.

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(4), P. 1526 - 1526

Published: Feb. 11, 2025

CYP199A4 is a cytochrome P450 and can catalyze the hydroxylation of 4-propionylbenzoic acid (4-pIBA) to generate α-hydroxyketone with high stereoselectivity. The F182L mutant (F182L-CYP199A4) has been shown support cleavage C-C bond between carbonyl hydroxyl groups α-hydroxyketone, whereas wild-type cannot. To uncover how Phe182 regulates substrate reactivity, we conducted classical molecular dynamics (MD) quantum mechanics/molecular mechanics (QM/MM) MD simulations on these systems. results predicted that formation preferentially led (S)-enantiomer. Moreover, findings revealed F182L-CYP199A4 facilitated hydrogen reactive peroxoanion (POA) species. This interaction stabilized near POA promoted subsequent cleavage. mechanism were elucidated by employing hybrid density functional theory (DFT). involved C-H 4-pIBA rate-limiting energy barrier 17.1 kcal/mol. catalyzed occurred via radical attack mechanism.

Language: Английский

Citations

0