Cited by Current State-of-Art in the Guerbet-Type β-Alkylation of Secondary Alcohols with Primary Alcohols Catalyzed by Complexes Based on 3d Metals

Recent advances on cross-coupling of alcohols via borrowing hydrogen catalysis DOI

Suteerna Mullick,

Adrija Ghosh, Debasis Banerjee

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(30), P. 4002 - 4014

Published: Jan. 1, 2024

This article highlights the recent advances and significance of β-alkylation reactions towards synthesis higher order alcohols.

Language: Английский

Citations

The importance of alkali cations in manganese-catalyzed enantioselective transfer hydrogenation of ketones: An insight into the effect of “NH” and “C N” groups in ligands DOI

Zechen Wang, Yuanyuan Wang,

Quanming Lyu

et al.

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115998 - 115998

Published: Feb. 1, 2025

Language: Английский

Citations

NNN manganese complex-catalyzed α-alkylation of methyl ketones using alcohols: an experimental and computational study DOI

Sachin Jalwal,

Anitta Regina,

Vaishnavi Atreya

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(7), P. 3236 - 3243

Published: Jan. 1, 2024

A quinoline-based pincer Mn catalyst for α-alkylation of methyl ketones using primary alcohols as alkyl surrogates is presented. The C–C bond formation reaction proceeds via a hydrogen auto-transfer protocol, generating water the only by-product.

Language: Английский

Citations

Direct Synthesis of Gem-β,β′-Bis(alkyl) Alcohols Using Nickel Catalysis via Sequential DCR Approach DOI

Lalit Mohan Kabadwal, Atanu Bera, Debasis Banerjee

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4018 - 4029

Published: Feb. 28, 2024

Chemoselective synthesis of functionalized gem-β,β′-bis(alkyl)alcohols by coupling a β-alkylated secondary alcohol with primary is reported using nickel via sequential DCR (dehydrogenation–condensation–rehydrogenation) approach. Using our method, 1-arylethanol and benzyl alcohols undergo one-pot successive double alkylation reaction to form alcohols. Methanol, C2–C12 alcohols, citronellol, fatty acid-derived oleic are tolerated, including late-stage functionalization steroid hormones (cholesterol testosterone) 5-pregnen-3β-ol-20-one. The catalytic transformations enabled the donepezil drug (used for Alzheimer's disease), N-heteroarenes (quinoline acridine), chromane intermediate flavan derivatives. Hammett kinetic plot analysis differently p-substituted 1-phenyl propanol indicated that oxidation might be rate-determining step expected strong influence substitution on kinetics. A negative ρ value (−0.60) strongly signify formation positive charge alcohol. Preliminary mechanistic investigation revealed dehydrogenation aldehyde as it involves C–H/D bond breaking alcohol, PH/PD 6.0 was calculated. Reaction profile studies, EPR experiments, Hammett-plot cyclic voltammetry, UV–visible XPS analysis, structural electronic changes at Ni-center well behavior catalysts during progress reactions.

Language: Английский

Citations

Ruthenium-catalyzed β-alkylation of secondary alcohols with primary alcohols: Protic N-heterocyclic carbene's promotional influence DOI

Jing Shi,

Lizhu Zhang,

Panpan Li

et al.

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1305, P. 137815 - 137815

Published: Feb. 17, 2024

Language: Английский

Citations

Efficient net transfer-dehydrogenation of glycerol: NNN pincer–Mn and manganese chloride as a catalyst unlocks the effortless production of lactic acid and isopropanol DOI

Akshara Bisarya,

Sunil Dhole,

Akshai Kumar

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(30), P. 12698 - 12709

Published: Jan. 1, 2024

Herein, a series of pincer-Mn complexes based on bis(imino)pyridine ligands the type

Language: Английский

Citations

Production of Lactic Acid via Catalytic Transfer Dehydrogenation of Glycerol Catalyzed by Base Metal Salt Ferrous Chloride and Its NNN Pincer-Iron Complexes DOI

Babu Venkateshappa,

Akshara Bisarya,

Pran Gobinda Nandi

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(33), P. 15294 - 15310

Published: Aug. 7, 2024

NNN-Bis(imino) pyridine-based pincer-Fe(II) complexes with an expected trigonal bipyramidal (TBP) geometry equilibrated to a rearranged ion pair of octahedral dicationic Fe complex containing two bis(imino)pyridine ligands that are neutralized by tetrahedral dianionic-[FeCl4]2–. Single-crystal X-ray diffraction (SCXRD), high-resolution mass spectrometry (HRMS), and UV–visible (UV–vis) studies suggested the equilibrium was dictated sterics R group on imine N, less-crowded groups tilting bulky ones favoring TBP geometry. Electron paramagnetic resonance (EPR) Evan's magnetic moment measurements indicated were Fe(II) in high-spin state. In solution, over period 7 days, these oxidized mixture low-spin Fe(III) species. These found be highly active toward transformation biodiesel waste glycerol value-added lactic acid (LA). Particularly, (Ph2NNN)FeCl2 (0.1 mol %) gave 91% LA 99% selectivity at 140 °C using 1.2 equiv NaOH. With 0.0001 % (Ph2NNN)FeCl2, very high turnovers (74% LA, 98% selectivity, 740 000 turnover number (TON) 4405 per hour (TOs/h)) obtained after days. EPR species catalyst, few which detected HRMS. Experiments Hg suggestive mostly homogeneous molecular nature catalyst minor contribution from heterogeneous nanoparticles.

Language: Английский

Citations

Pincer–Ruthenium-Catalyzed β-Methylation of Alcohols DOI

Pran Gobinda Nandi,

Raksh V. Jasra, Akshai Kumar

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(21), P. 3138 - 3152

Published: Oct. 30, 2023

The synthesis and characterization of three NNN pincer–Ru complexes based on bis(imino)pyridine ligands have been reported. These along with other previously reported catalysts 2,6-bis(benzimidazol-2-yl)pyridine employed to accomplish the β-methylation 2-phenylethanol selective β-dimethylation 1-phenylethanol using methanol as an alkylating agent. In general, pincer–ruthenium complex [(MeBim2NNN)RuCl(PPh3)2]Cl dimethyl-substituted ligand was found be most efficient among considered catalysts. Under best conditions, in (0.5 mol %)-catalyzed reactions presence 0.75 equiv KOH 7.5 methanol, up 92% yield β-methylated obtained at 140 °C. On hand, could achieved 2 Na 24.8 methanol. developed synthetic protocol is generic nature applied about 35 substrates. reaction has also probed from a mechanistic point view. While mercury poisoning experiments revealed catalyzed by well-defined molecular catalysts, kinetic indicated that rate product formation linear dependence concentrations both catalyst 2-phenylethanol. DFT studies complement observed secondary isotope effect (KIE) 1.56 suggest dehydrogenolysis involving σ-bond metathesis Ru–H species leading evolution hydrogen rate-determining step barrier 24.06 kcal/mol. Ru–OMe species, being lowest-energy intermediates catalytic cycle, are likely resting state cycle detected NMR HRMS analysis.

Language: Английский

Citations

Reforming of ethanol to hydrogen and acetic acid catalyzed by pincer-ruthenium complexes DOI

Vinay Arora,

Sunil Dhole,

Akshai Kumar

et al.

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(23), P. 6699 - 6711

Published: Jan. 1, 2023

Herein, we report the exceptional activity of pincer-ruthenium catalysts in value-addition ethanol via its high yield conversion ( ca. 73%) to green hydrogen and precious acetic acid with selectivity 100%) under ambient conditions.

Language: Английский

Citations

Synthesis and reactivity of isomeric Ru complexes with hydroxypyridyl fragment: active catalysts for β‑alkylation of secondary alcohols with primary alcohols DOI

Jing Shi, Panpan Li, Chunjian Qi

et al.

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1321, P. 140159 - 140159

Published: Sept. 23, 2024

Language: Английский

Citations