Advances in Group VI Metal‐Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions DOI Open Access

Tushar Singh,

Vaishnavi Atreya,

Sachin Jalwal

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(23)

Published: Oct. 10, 2023

Transition metal-catalyzed homogeneous hydrogenation and dehydrogenation reactions for attaining plethora of organic scaffolds have evolved as a key domain research in academia industry. These protocols are atom-economic, greener, line with the goal sustainability, eventually pave way numerous novel environmentally benign methodologies. Appealing progress has been achieved realm catalysis utilizing noble metals. Owing to their high cost, less abundance along toxicity issues led scientific community search sustainable alternatives. In this context, earth- abundant base metals gained substantial attention culminating enormous recent years, predominantly pincer-type complexes nickel, cobalt, iron, manganese. regard, group VI chromium, molybdenum tungsten overlooked remain underdeveloped despite earth-abundance bio-compatibility. This review delineates comprehensive overview arena homogeneously catalysed (de)hydrogenation using molybdenum, till date. Various described; hydrogenation, transfer dehydrogenation, acceptorless dehydrogenative coupling, hydrogen auto transfer, scope brief mechanistic insights.

Language: Английский

Copper-Mediated C4-Benzylations of 5-Aminopyrazoles with 3-Indoleacetic Acids DOI
Qiwen Gao, Jinhong Tian,

Kangmei Wen

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 6623 - 6632

Published: May 11, 2023

Herein, we present a copper-mediated C4-benzylation of 5-aminopyrazoles with 3-indoleacetic acids. Various benzylated are prepared in good-to-excellent yields under basic and ligand-free conditions the presence copper acetate. Moreover, this benzylation method is applicable to other substrates, including naphthylamine, 2-aminochromen-4-one, enamines. Some products exhibit antiproliferative activities against cancer cell lines. In addition, C4-benzylated cyclized into 1H-pyrazolo[4',3':6,7]azepino[3,4-b]indoles aldehydes via one-pot two-step processes; notably, fluorescence emissions large Stokes shifts.

Language: Английский

Citations

12
Selective N-Alkylation of Aminobenzenesulfonamides with Alcohols for the Synthesis of Amino-(N-alkyl)benzenesulfonamides Catalyzed by a Metal–Ligand Bifunctional Ruthenium Catalyst DOI

Lu Shen,

Xingliang Wu,

Lili Shi

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8397 - 8406

Published: June 3, 2024

[(

Citations

4
Cathodic Deoxygenative Alkylation of Nitro(hetero)arenes with Organic Halides DOI
Ziliang Wang, Jianfeng Zhou,

Z. M. Wang

et al.

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

Published: Jan. 28, 2025

We have realized a cathodic deoxygenative alkylation between nitro(hetero)arenes and organic halides, employing bis(pinacolato)diboron (B2pin2) LiCl as additives to trap stabilize the generated alkyl radicals carbanions, thereby facilitating efficient N-O cleavage selective C-N bond formation. The protocol offers an economical method for synthesis of multiple aromatic(hetero) amines, without need reactive reductants exclusion air moisture. Notably, is distinguished by scalability, broad functional group compatibility, safe mild conditions, demonstrating practicality in late-stage modification various bioactive compounds.

Language: Английский

Citations

0
Bio-waste derived Ag/chitin nanocatalyst induces green and efficient N-alkylation of alcohols with amines via borrowing hydrogen strategy DOI
Yu Huang, Yan Li, Qiudi Zhu

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160587 - 160587

Published: Feb. 1, 2025

Language: Английский

Citations

0
Ruthenium‐Catalyzed α‐Alkylation of Arylacetonitriles with Primary Alcohols: N‐heterocyclic Carbene‐Amine's Promotional Influence DOI

Xurui Wei,

Xiuju Cai,

Ming Huang

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(7)

Published: Feb. 1, 2025

Abstract Transition‐metal‐catalyzed α‐alkylation of nitriles with alcohols is an environmentally benign reaction, and the development simple efficient catalysts for this transformation a growing area research. In study, we report serial bidentate N ‐heterocyclic carbene (NHC) ruthenium complexes different extra donors alcohols. Through adjusting backbone NHC ligands, catalytic activities these could be controlled. The complex ( Ru3 ) bearing amine donor benzimidazolium exhibited highest activity. A large variety α‐alkylated were obtained in 30%–88% yields, by using 1 mol% amount Cs 2 CO 3 (20 mol%). Detailed control experiments deuterium‐labeling suggested that reaction proceeds via borrowing hydrogen pathway.

Language: Английский

Citations

0
Molybdenum‐Catalyzed Asymmetric Amination of α‐Hydroxy Esters: Synthesis of α‐Amino Acids DOI Creative Commons
Shahida Perveen, Talat S. Rahman, Tariq Ali

et al.

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

Published: March 10, 2025

Abstract Unnatural α‐amino acids are found in a wide variety of bioactive compounds ranging from proteins to pharmaceutical agents materials science. As result, the investigation efficient and simple methods for their synthesis is major purpose reaction development. In this study, it that catalyst based on molybdenum, an earth‐abundant transition metal, can facilitate amination readily accessible α‐hydroxy esters afford N ‐protected unnatural acid high yield. This process also enables enantioselective amination, which proceeds through cooperative catalysis chiral molybdenum complex with phosphoric (CPA), complements earlier procedures catalytic important class compounds. The obtained protected ester products directly useful or further utilized commercially available drugs analogs.

Language: Английский

Citations

0
Unexpected activity of MgO nanoclusters for the reductive-coupling synthesis of organonitrogen chemicals with C = N bonds DOI Creative Commons
Ziliang Yuan, Bo Han, Bing Liu

et al.

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

Published: March 26, 2025

Reductive-coupling of nitro compounds and alcohols is a sustainable route for constructing C = N bonds in organonitrogen chemicals, yet challenging due to the inertness α-Csp3-H bond vulnerability towards hydrogenation. Here, we report surprising catalytic activity ultrafine alkaline-earth metal oxide MgO nanoclusters (0.9 ± 0.3 nm) that efficiently activate bonds, facilitating transfer hydrogenation synthesis value-added chemicals bearing with high excellent yields (86–99%). Controlled experiments characterizations showed crucial role oxygen vacancies (Ov) local Mg environment (Mg-O bond) substrate adsorption activation via electronic interactions between substrate's negatively charged atoms Ov sites nanoclusters. Theoretical calculation further confirmed significantly lowered energy barrier hydrogen atom from ethanol group nitrobenzene (29.3 vs. 52.9 kcal/mol), which rate-determining step highest reductive-coupling reactions. Our method not only provides an efficient pathway synthesizing but also inspires exploration main element catalysts as alternatives transition noble organic transformations. The reductive coupling typically amine products. Here authors show catalyse this reaction, giving unsaturated containing

Language: Английский

Citations

0
Iridium-Catalyzed Monoamination of Polyols toward Amino Alcohols or Amino Acids DOI

Lingyun Shen,

Jiajie Wu, Qingshu Zheng

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8049 - 8059

Published: April 30, 2025

Language: Английский

Citations

0
Synergetic roles of pyridinic nitrogen and carbonyl sites in nitrogen-doped carbon for the metal-free transfer hydrogenation reactions DOI

Xiaomei Lu,

Jie He, Liang Huang

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 324, P. 122277 - 122277

Published: Dec. 9, 2022

Language: Английский

Citations

18
Selective Monoalkylation or Dialkylation of Indenes with Alcohols by Bis-N-Heterocyclic Carbene Manganese DOI

Ning Wang,

Yinwu Li, Zhe Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18032 - 18044

Published: Nov. 22, 2024

Selective direct alkylation of indenes is important for the synthesis and decoration indene derivatives. In contrast to traditional methods, using unactivated alcohol as reagents via borrowing hydrogen or autotransfer highly attractive. However, nature high-lying lowest unoccupied molecular orbital condensation intermediate raises a big challenge development BH system alcohols. Through tuning stability reactivity metal-hydride species by theoretical prediction, herein, we succeeded in developing non-noble Mn-catalyzed selective monoalkylation dialkylation under mild conditions, producing corresponding versatile alkylated satisfactory yields. A broad scope substrates including primary benzylic, aliphatic, amino, hydroxyl, second alcohols well various are tolerated system. Additionally, this method could be used potential precatalyst complexes bioactive molecules. Mechanistic studies control experiments, kinetic investigations, isotope effect, deuterium labeling density functional theory calculations, reveal proper successful process.

Language: Английский

Citations

3