Nickel-catalyzed alkylation of ketones and nitriles with primary alcohols

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(48), P. 9753 - 9762

Published: Jan. 1, 2022

Nickel( ii )–salphen catalyzed α-alkylation of ketones and nitriles with primary alcohols has been developed.

Language: Английский

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Nickel–PNN catalysed sustainable synthesis of polysubstituted quinolines under microwave irradiation

Catalysis Science & Technology, Journal Year: 2024, Volume and Issue: 14(20), P. 5959 - 5969

Published: Jan. 1, 2024

This manuscript describes the synthesis of triazolyl-pyridine-based pincer cationic and neutral nickel complexes their application in microwave-assisted quinolines.

Language: Английский

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TiO₂ (P25) nanoparticle catalyzed C-alkylation and quinoline synthesis via the borrowing hydrogen method

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(18), P. 8751 - 8758

Published: Jan. 1, 2023

TiO 2 (P25) nanoparticle catalyzed C-alkylation and quinoline synthesis via the borrowing hydrogen method.

Language: Английский

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Efficient Synthesis of Benzimidazole and Quinoline Derivatives Catalyzed by Functionalized Amidato Ruthenium Complexes in Water via Acceptorless Dehydrogenative Coupling Strategy

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(16)

Published: July 10, 2023

Abstract Transition‐metal‐catalyzed acceptorless dehydrogenative coupling (ADC) has emerged as a sustainable synthetic strategy for the construction of N ‐heteroaromatics. Herein, series water‐soluble amidato Ru catalysts were designed, synthesized, and utilized in selective synthesis 2‐substituted benzimidazoles from aromatic diamines primary alcohols, well quinolines substituted 2‐aminobenzyl alcohols acetophenones via ADC water. Catalyst 1 d bearing strong electron‐donating hydroxyl group on ligand exhibited best catalytic activity. The system demonstrated remarkable efficiency versatility, allowing application over 40 substrates two reactions with good to high yields. Based control experiments density functional theory (DFT) calculations, plausible mechanism was proposed, highlighting significant role functionalized complexes catalyzing alcohol dehydrogenation an outer‐sphere pathway.

Language: Английский

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Quantum-Chemical Study of the Assembly Mechanism of 1-Pyrrolines from N-Benzylaldimines and Arylacetylenes in KO^tBu/DMSO Superbasic Medium

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 7058 - 7069

Published: May 23, 2023

By using a quantum-chemical approach, B2PLYP-D2/6-311+G**//B3LYP/6-31+G*, we have carried out detailed study of the assembly 1-pyrrolines from N-benzyl-1-phenylmethanimine and phenylacetylene in superbasic medium KOtBu/dimethyl sulfoxide (DMSO). In this way, considered, both theoretically experimentally, mechanisms through concerted stepwise nucleophilic cycloaddition addressed side processes accompanying assembly. It is found that via kinetically more favorable than cycloaddition. At same time, reaction C-vinylation aldimine with occurs similar activation energy as leads to formation 2-aza-1,4-pentadiene. The anion 2-aza-1,4-pentadiene an intermediate for leading triarylpyridines 1,3-diarylpropan-1-ones. Triarylpyridines are formed next molecule 2-aza-1,4-pentadiene, while 1,3-diarylpropan-1-ones result hydrolysis 2-aza-1,4-pentadienes. mild conditions (60 °C, 15 min) relate complexes KOtBu/DMSO medium, where readily accessible attack by molecule.

Language: Английский

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Cu–ABNO Catalyst for the Synthesis of Quinolines and Pyrazines via Aerobic Double Dehydrogenation of Alcohols

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

Published: Nov. 28, 2024

In this report, a new imidazole- and amide-functionalized pincer-like Cu(II) complex (1) was synthesized characterized. By employing 1 9-azabicyclo[3.3.1]nonane NH-Oxyl (ABNOH), catalytic protocol for alcohol oxidation the subsequent oxidation-triggered synthesis of quinolines pyrazines were explored. Alcohols such as 2-aminoaryl alcohols also oxidized efficiently. As carbonyls from 2-arylaminobenzyl secondary are synthons quinolines, we explored their directly alcohols. The quite efficient completed reaction in only ∼5–10 h. Combinations (a) primary with or ketones (b) found to be very effective quinolines. successful various 1,2-diols 1,2-diaminobenzenes 10 Mechanistic investigations showed that generated acted an active catalyst: it activated O2 subsequently cooperation N-Oxyl (ABNO•) α-CH hydrogen coordinated alkoxide. Then, Cu(II)/Cu(I) reduction led formation carbonyl compounds, which via successive C–C/C–N coupling reactions resulted heterocycles presence KOtBu 1.

Language: Английский

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Co‐Catalyzed Metal‐Ligand Cooperative Approach for N‐alkylation of Amines and Synthesis of Quinolines via Dehydrogenative Alcohol Functionalization

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(29)

Published: Aug. 1, 2023

Abstract Herein we report a cobalt‐catalyzed sustainable approach for C−N cross‐coupling reaction between amines and alcohols. Using well‐defined Co‐catalyst 1 bearing 2‐(phenyldiazenyl)‐1,10‐phenanthroline ligand, various N ‐alkylated were synthesized in good yields. efficiently alkylates diamines producing , N′ ‐dialkylated yields showed excellent chemoselectivity when oleyl alcohol β‐citronellol, containing internal carbon‐carbon double bond used as alkylating agents. is equally compatible with synthesizing ‐heterocycles via dehydrogenative coupling of H ‐Indole was an intramolecular ‐alkylation reaction, substituted quinolines by 2‐aminobenzyl secondary A few control reactions spectroscopic experiments conducted to illuminate the plausible mechanism, indicating that ‐catalyzed proceeds through borrowing hydrogen pathway. The coordinated arylazo ligand participates actively throughout reaction; eliminated during dehydrogenation alcohols set aside backbone subsequently gets transferred reductive amination step imine intermediates yielding amines. On other hand, quinoline synthesis followed successive C−C steps forming 2 O by‐product under air.

Language: Английский

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N‐alkylation of benzamides/sulfonamides using alcohols via borrowing hydrogen approach by well‐defined Pd (II) pincer complexes

Applied Organometallic Chemistry, Journal Year: 2023, Volume and Issue: 37(10)

Published: Aug. 22, 2023

The development of green, sustainable, and atom‐economical procedure for the construction amides via C‐N bond formation is a high priority in synthetic organic community. In this research article, we demonstrate simple an efficient catalytic protocol N‐alkylation benzamides/sulfonamides using aromatic primary alcohols as coupling partners through borrowing hydrogen (BH) strategy by employing newly constructed palladium (II) O^N^O pincer complexes. All complexes are characterized analytical spectral methods (FT‐IR, NMR, HRMS). Further, solid‐state molecular structures have been well authenticated single‐crystal XRD studies. present facile, worked low catalyst loading (0.5 mol%), furnishes desired N‐alkyl with excellent yields up to 92%. methodology, reaction proceeds intermediates such aldehyde (E)‐N‐benzylidenebenzamide release water ecological by‐product. control experiments plausible mechanistic investigations suggested that was initially dehydrogenation alcohol generate alkylated products auto‐transfer. A large‐scale synthesis N‐(4‐methoxybenzyl)benzamide proves effectiveness Pd catalysts.

Language: Английский

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Ruthenium-Catalyzed Reductive Coupling of Epoxides with Primary Alcohols via Hydrogen Transfer Catalysis

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(1), P. 310 - 318

Published: Dec. 22, 2022

Herein, we report the ruthenium-catalyzed synthesis of β-alkylated secondary alcohols via regioselective ring-opening epoxides with feedstock primary alcohols. The reaction utilized alcohol as carbon source and terminal reductant. Kinetic labeling experiments elucidate hydrogen transfer catalysis that operates tandem Markovnikov selective hydrogenation transfer-mediated cross-coupling resulting substrates. A broad scope (40 examples including drugs/natural product derivatives) excellent regioselectivity for a variety substrates were shown.

Language: Английский

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Unveiling the Potential of SNS-Ni Complex for Establishing C–N Bonds: An Approach toward Chemoselectivity

Organometallics, Journal Year: 2024, Volume and Issue: 43(21), P. 2697 - 2702

Published: Oct. 7, 2024

Recent research has focused a lot on using the borrowing hydrogen (BH) approach to react amines with alcohols convert C–O bond into C–N bond. However, notion of chemoselectivity in BH-mediated N-alkylation rarely been studied. Herein, we have demonstrated application synthesized SNS-Ni complex constructing various bonds via coupling diverse alcohols. Delightfully, catalytic protocol also activates challenging C4–C16 aliphatic Aryl amino are selectively N-alkylated different alcohols, while keeping OH group intact alcohol portion. Furthermore, without reducing distal unsaturation, technique was successfully employed for chemoselective fatty The preliminary mechanistic investigation suggests alkylation occurs nonradical pathway.

Language: Английский

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