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

Chemical Communications, Год журнала: 2024, Номер 60(30), С. 4002 - 4014

Опубликована: Янв. 1, 2024

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

Язык: Английский

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Recent Development in Synthesis of N‐Methylamines with Amines and Methanol

ChemCatChem, Год журнала: 2024, Номер 16(16)

Опубликована: Март 23, 2024

Abstract The N‐methylation reaction of amines with methanol via the borrowing‐hydrogen strategy is an important method for construction C−N bonds. Compared other C1 sources, such as toxic formaldehyde or expensive formic acid, more suitable reactions due to its eco‐friendliness and low price. Using this strategy, various types N‐methylated products, including biological pharmaceutical molecules have been prepared. Here, we present a thorough survey decades articles showing current developments in methanol. We discuss homogenous, heterogenous light‐driven catalytic systems both N,N‐dimethylation reactions. This review presents shortcomings provides future development progress

Язык: Английский

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Mo2C Catalyst Leads to Highly Efficient Hydrogen Transfer of Alcohols and Amines to Synthesize N-alkylamines

Chemical Communications, Год журнала: 2024, Номер 60(93), С. 13750 - 13753

Опубликована: Янв. 1, 2024

Highly efficient hydrogen transfer coupling of alcohols and amines achieved by molybdenum carbide.

Язык: Английский

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Role of ancillary ligands in selectivity towards acceptorless dehydrogenation versus dehydrogenative coupling of alcohols and amines catalyzed by cationic ruthenium(ii)–CNC pincer complexes

Dalton Transactions, Год журнала: 2023, Номер 52(43), С. 15878 - 15895

Опубликована: Янв. 1, 2023

An unexpected reversal in catalytic activity for acceptorless dehydrogenative coupling compared to alcohol dehydrogenation has been observed using a series of cationic Ru(II)-CNC pincer complexes with different ancillary ligands. In continuation our study 1a-6a, new bulky N-wingtips [Ru(CNCiPr)(CO)(PPh3)Br]PF6 (1b), [Ru(CNCCy)(CO)(PPh3)Cl]PF6 (1c), [Ru(CNCCy)(CO)(PPh3)H]PF6 (2c), [Ru(CNCiPr)(PPh3)2Cl]PF6 (3b), [Ru(CNCCy)(PPh3)2Cl]PF6 (3c), [Ru(CNCiPr)(PPh3)2H]PF6 (4b), [Ru(CNCCy)(PPh3)2H]PF6 (4c), [Ru(CNCiPr)(DMSO)2Cl]PF6 (6b), and [Ru(CNCCy)(DMSO)2Cl]PF6 (6c) [CNCR = 2,6-bis(1-alkylimidazol-2-ylidene)-pyridine] have synthesized the activities their N-methyl analogues transfer hydrogenation cyclohexanone benzyl alcohol. Furthermore, all utilized as catalysts reaction amines. While were found be line previously trend based on ligands (CO > COD DMSO PPh3), reaction, containing PPh3 performed better CO Based NMR mass investigation reactions, plausible mechanism suggested explain difference its during reaction. substrate scope wide range amines explored, including synthesizing some pharmaceutically important imines. All characterized by various spectroscopic techniques, structures 4b 6b confirmed single-crystal X-ray diffraction technique.

Язык: Английский

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Ruthenium NNN‐Based Pincer Complexes with Metal Ligand Cooperation as Catalysts for N‐Methylation of Anilines and Nitroarenes with Methanol as a C1 Source

ChemCatChem, Год журнала: 2024, Номер 16(12)

Опубликована: Фев. 26, 2024

Abstract A novel phosphine‐free ruthenium pincer complex based on an NNN ligand has been prepared and fully characterized. The was subsequently employed as efficient catalyst for the N‐methylation of amines direct nitroarenes using methanol a C1 source under mild reaction conditions following borrowing‐hydrogen approach. Both catalytic transformations were performed with only amounts base closed air without any other additives.

Язык: Английский

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Manganese-catalyzed oxidation of furfuryl alcohols and furfurals to efficient synthesis of furoic acids

RSC Advances, Год журнала: 2024, Номер 14(37), С. 27060 - 27065

Опубликована: Янв. 1, 2024

Herein, the direct oxidation of furfuryl alcohols and furfurals to corresponding furoic acids is performed highly efficiently with potassium hydroxide as base in presence a catalytic amount PNP pincer manganese catalyst dioxane.

Язык: Английский

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Catalytic N-Alkylation of (Hetero)Aromatic Amines and Tandem Annulation Reactions

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(20), С. 14720 - 14739

Опубликована: Окт. 7, 2024

A general and practical approach for N-alkylation of heteroaromatic amines with alcohols is always challenging rarely reported. Here, we designed synthesized phosphine-free, robust, efficient N,N-bidentate-Co(II) complexes a universal strategy. This present catalytic methodology can be applied to wide range substrates by varying alcohols, including aryl, aliphatic, acyclic, cyclic groups, such as aminopyridine, 2-aminopyrimidine, aminoquinoline provide diverse monoalkylated organonitrogen compounds in good excellent yields (108 examples). In addition, the utility developed protocol was also extended successfully dehydrogenative synthesis biologically important quinoline derivatives (11 Particularly, 8-aminoquinoline reacted differently tandem N-alkylated-transfer hydrogenative byproduct (N-benzyl-1,2,3,4-tetrahydroquinolin-8-amine) obtained, revealing activity complex I. The reaction proceeded under environmentally benign conditions, which liberates water sole byproduct. Notably, concise acetylcholinesterase inhibitors (AChEIs) scaffolds potential cognition enhancers illustrated protocol. Interestingly, various control deuterium-labeled experiments were performed, suggesting that proceeds via borrowing hydrogen pathway.

Язык: Английский

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Catalytic Fe2+ Cation Pair Site for Base‐free N‐Alkylation of Aromatic Amines with Alcohols

ChemSusChem, Год журнала: 2024, Номер unknown

Опубликована: Окт. 11, 2024

The development of heterogeneous Fe catalysts is very attractive due to the ubiquitous, abundant, and inexpensive nature as a resource. However, oxides are commonly inert hence, design fabrication active sites essential. Herein, an cation pair site by simple reduction treatment SiO

Язык: Английский

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Radical‐driven imine hydrogenation promoted by the cooperativity of nickel and a redox‐active ligand

European Journal of Inorganic Chemistry, Год журнала: 2024, Номер 28(2)

Опубликована: Окт. 23, 2024

Abstract In the case of N‐alkylation reaction via borrowing hydrogen (BH) methods, imine hydrogenation is one critical steps. Mechanistically, majority hydrogenation, either by dihydrogen gas or alcohol in BH follow two‐electron chemistry, where a metal‐hydride intermediate plays pivotal role. Herein we demonstrate completely complementary protocol, governed radical pathway. Such pathway adopted from redox active nature azophenolate ligand backbone. The facile and reversible 2e − /2H + , azo/hydrazo couple nickel catalyst helps storing dehydrogenation. An substrate reduced one‐electron azo motif with assistance center. drives atom transfer step hydrazo to conduct hydrogenation. A set kinetics experiments including Eyring analysis, inhibition experiment along computational probation attest for radical‐promoted mechanism.

Язык: Английский

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Alkali‐Mediated/Catalyzed Transition‐Metal‐Free Tandem Reaction Triggered by the Borrowing Hydrogen and Aerobic Dehydrogenation Processes of Alcohols

ChemistrySelect, Год журнала: 2024, Номер 9(40)

Опубликована: Окт. 1, 2024

Abstract The transformation of alcohols to important classes compounds is a central topic in chemistry because they are abundant, renewable, and attractive building blocks. alkali‐mediated/catalyzed borrowing hydrogen aerobic dehydrogenation processes open new sustainable access for the alcohol conversion under transition‐metal‐free conditions. In this review, we summarize recent sequential reactions involving alcohols. Furthermore, review not only introduces tentative pathways these transformations, but also discusses role alkali, solvent effects, substrate reactivity on reactions.

Язык: Английский

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