Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(22), P. 15013 - 15053

Published: Nov. 6, 2023

Methanol is a fundamental feedstock and widely used in the chemical petroleum industries. It can serve as C1 source to make variety of C–C C–N bond formation dehydrogenative coupling products, which have important applications natural products drug discovery. A high hydrogen content (12.5 wt%) methanol makes it an effective H2 donor for transfer hydrogenation various reducible functional groups. plethora transition metal-based processes been developed using methanol. Notably, recent review articles focused on aspect However, more updated that examines challenges both C1-source H2-source organic transformations contributing concept economy has not presented yet. This Review summarizes (homogeneous, heterogeneous, photo-) catalyst system C-, N-, O-methylation ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, sulfonamides direct N-methylation nitro compounds under borrowing strategy N-formylation amines acceptorless dehydrogenation source. also covers insights into reaction mechanisms role carefully selected ligands metal catalysis activation incorporation -CD3, methylation molecules. Moreover, describes groups such aldehydes, alkynes, with detail.

Language: Английский

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Zn(II)‐Stabilized Azo‐Anion Radical Catalyzed Sustainable C−C Bond Formation: Regioselective Alkylation of Fluorene, Oxindole, and Indoles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(10)

Published: Feb. 7, 2024

Abstract Herein we report a sustainable approach for the alkylation of ketones, 9 H ‐fluorene, oxindole, and indole using alcohols as alkylating agent catalyzed by well‐defined air‐stable zinc catalyst ( 1 ) tridentate redox non‐innocent arylazo ligand, 2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline L ). 2–3 mol % efficiently produces substituted α‐alkylated 9‐alkylated fluorenes, C3 ‐alkylated oxindoles, indoles in moderate to good isolated yields. In aerial condition, formation bis(indolyl)methane (BIMs) derivatives were observed when subjected primary alcohols. A few drug molecules containing BIMs prepared The exhibited chemoselectivity during functionalization fluorene with oleyl alcohol β‐citronellol. control experiments, including deuterium labeling performed unveil reaction mechanism indicate that one‐electron reduced azo‐anion radical species [ ]‐formed situ, acts active catalyst. All events occur at redox‐active aryl‐azo which reservoir hydrogen electrons throughout catalytic cycle, keeping Zn(II)‐center template.

Language: Английский

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A Guide for Mono‐Selective N‐Methylation, N‐Ethylation, and N‐n‐Propylation of Primary Amines, Amides, and Sulfonamides and Their Applicability in Late‐Stage Modification

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(26)

Published: Feb. 14, 2024

Abstract This review provides a comprehensive overview of mono‐alkylation methodologies targeting crucial nitrogen moieties – amines, amides, and sulfonamides found in organic building blocks pharmaceuticals. Emphasizing the intersection chemical precision with drug discovery, central challenge addressed is achieving one‐pot mono‐selective short‐chain N‐alkylations (methylations, ethylations, n ‐propylations), preventing undesired overalkylation. Additionally, sustainable, safe, benign alternatives to traditional alkylating agents, including alcohols, carbon dioxide, carboxylic acids, nitriles, alkyl phosphates, quaternary ammonium salts, carbonates, are explored. review, categorized by nature agent, aids researchers selecting suitable methods for N‐alkylation.

Language: Английский

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Ruthenium Complexes with NNN-Pincer Ligands for N-Methylation of Amines Using Methanol

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(25), P. 11821 - 11831

Published: June 7, 2024

A series of ruthenium complexes (Ru1–Ru4) bearing new NNN-pincer ligands were synthesized in 58–78% yields. All the are air and moisture stable characterized by IR, NMR, high-resolution mass spectra (HRMS). In addition, structures Ru1–Ru3 confirmed X-ray crystallographic analysis. These Ru(II) exhibited high catalytic efficiency broad functional group tolerance N-methylation reaction amines using CH3OH as both C1 source solvent. Experimental results indicated that electronic effect substituents on considerably affects reactivity which Ru3 an electron-donating OMe showed highest activity. Deuterium labeling control experiments suggested dehydrogenation methanol to generate hydride species was rate-determining step reaction. Furthermore, this protocol also provided a ready approach versatile trideuterated N-methylamines under mild conditions CD3OD deuterated methylating agent.

Language: Английский

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Preparation of a novel cadmium-containing coordination polymer and catalytic application in the synthesis of N-alkylated aminoquinoline derivatives via the borrowing hydrogen approach

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(11), P. 5064 - 5072

Published: Jan. 1, 2024

Herein, we report an efficient and straightforward approach for the synthesis of

Language: Английский

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A sustainable strategic approach for N-alkylation of amines with activation of alcohols triggered via a hydrogen auto-transfer reaction using a Pd(ii) complex: evidence for metal–ligand cooperativity

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(20), P. 8740 - 8749

Published: Jan. 1, 2024

This work describes a new well-defined, air-stable, phosphine free palladium(II) [Pd(L)Cl] (1) catalyst. catalyst was utilized for

Language: Английский

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N-alkylation of Amines with primary/secondary alcohols using novel Cobalt(II) inverse triazolyl-pyridine complex

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(65), P. 8581 - 8584

Published: Jan. 1, 2024

Herein, we report a highly effective homogeneous methodology for the

Language: Английский

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A well-defined phosphine free metal-ligand cooperative route for N-alkylation of aromatic amines via activation of renewable alcohols catalyzed by a NNN pincer cobalt(II) complexes

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Two cobalt( ii ) complexes C1 and C2, supported by an NNN pincer, were synthesized, characterized with various techniques. These utilized to study catalytic activity in the N -alkylation of amines via borrowing hydrogen strategy.

Language: Английский

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The recyclable non-metal acid-catalyzed ammination of benzyl alcohol

Sustainable Chemistry and Pharmacy, Journal Year: 2025, Volume and Issue: 44, P. 101957 - 101957

Published: March 3, 2025

Language: Английский

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Synthesis, Characterization and Application of NNN Pincer Manganese Complexes with Pyrazole Framework in α-Alkylation Reaction

Molecules, Journal Year: 2025, Volume and Issue: 30(7), P. 1465 - 1465

Published: March 26, 2025

A series of novel NNN pincer manganese complexes based on pyrazole skeleton 4 were efficiently synthesized in a two-step process. All the new fully characterized by 1H, 13C NMR spectra. Furthermore, molecular structures 4a and 4c also determined X-ray single-crystal diffraction. The manganese(I) catalysts obtained showed efficient catalytic activity α-alkylation reaction ketones with alcohols. Under optimal conditions, expected products procured moderate to high yields.

Language: Английский

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