Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

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N-Alkylation of Amines by C1–C10 Aliphatic Alcohols Using A Well-Defined Ru(II)-Catalyst. A Metal–Ligand Cooperative Approach

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5944 - 5961

Published: April 13, 2023

A Ru(II)-catalyzed efficient and selective N-alkylation of amines by C1-C10 aliphatic alcohols is reported. The catalyst [Ru(L1a)(PPh3)Cl2] (1a) bearing a tridentate redox-active azo-aromatic pincer, 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (L1a) air-stable, easy to prepare, showed wide functional group tolerance requiring only 1.0 mol % (for N-methylation N-ethylation) 0.1 loading for with C3-C10 alcohols. array N-methylated, N-ethylated, N-alkylated were prepared in moderate good yields via direct coupling 1a efficiently catalyzes the diamines selectively. It even suitable synthesizing using (aliphatic) diols producing tumor-active drug molecule MSX-122 yield. excellent chemo-selectivity during oleyl alcohol monoterpenoid β-citronellol. Control experiments mechanistic investigations revealed that 1a-catalyzed reactions proceed borrowing hydrogen transfer pathway where removed from dehydrogenation step stored ligand backbone 1a, which subsequent steps transferred situ formed imine intermediate produce amines.

Language: Английский

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CrCl₂-catalyzed α-alkylation of carbonyl compounds via a borrowing hydrogen approach

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 1955 - 1962

Published: Jan. 1, 2024

A new and efficient catalytic system for sustainable α-alkylation of carbonyl compounds with alcohols via a borrowing hydrogen strategy is presented.

Language: Английский

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Biogenic synthesis of δ‐MnO₂ nanoparticles: A sustainable approach for C‐alkylation and quinoline synthesis via acceptorless dehydrogenation and borrowing hydrogen reactions

Applied Organometallic Chemistry, Journal Year: 2023, Volume and Issue: 37(7)

Published: April 26, 2023

The sustainable and environmentally benign biogenic synthesis of manganese‐oxide nanoparticles (MnO 2 NPs) in a single crystalline δ ‐phase its subsequent synthetic utility have been described. synthesized ‐MnO NPs were characterized using scanning electron microscopy (SEM), energy dispersive X‐ray (EDX), diffraction (XRD) analysis techniques. detailed envisages the reduction Mn(VII) to Mn(IV) was facilitated by various phytochemicals present aq. mango leaves extract, avoiding use external ligand source. perceived delta ( ) monoclinic phase, wherein spherical agglomerated morphology displayed with particle size <5 nm. Further, newly developed showcased for alpha‐keto‐alkylation quinoline via hydrogen autotransfer acceptorless dehydrogenative coupling strategy. Moreover, series control experiments, mechanistic elucidation, catalyst recyclability, dye removal study demonstrated.

Language: Английский

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Nickel-Catalyzed α-Alkylation of Arylacetonitriles with Challenging Secondary Alcohols

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(10), P. 6664 - 6676

Published: Jan. 3, 2023

Nickel(II) complex 1 was utilized as a sustainable catalyst for α-alkylation of arylacetonitriles with challenging secondary alcohols. Arylacetonitriles wide range functional groups were tolerated, and various cyclic acyclic alcohols to yield large number α-alkylated products. The plausible mechanism involves the base-promoted activation precatalyst an active 2 (dehydrochlorinated product) which activates O–H C–H bonds alcohol in dehydrogenative pathway.

Language: Английский

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A strategic approach for Csp³–H functionalization of 9H-fluorene: an acceptorless dehydrogenation and borrowing hydrogen approach

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(3), P. 611 - 617

Published: Jan. 1, 2023

Herein, we described the selective synthesis of both alkylated and alkenylated fluorenes using a single SNS ligand derived nickel complex.

Language: Английский

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Nickel‐Catalyzed Chemodivergent Coupling of Alcohols: Efficient Routes to Access α,α‐Disubstituted Ketones and α‐Substituted Chalcones

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(15)

Published: Jan. 17, 2024

Abstract Chemodivergent (de)hydrogenative coupling of primary and secondary alcohols is achieved utilizing an inexpensive nickel catalyst, (6‐OH‐bpy)NiCl 2 . This protocol demonstrates the synthesis branched carbonyl compounds, α , ‐disubstituted ketones, ‐substituted chalcones via borrowing hydrogen strategy acceptorless dehydrogenative coupling, respectively. A wide range aryl‐based are coupled with various in this tandem dehydrogenation/hydrogenation reaction. The along KO t Bu or K CO 3 governed selectivity for formation saturated ketones chalcones. preliminary mechanistic investigation confirms reversible dehydrogenation to carbonyls metal‐ligand cooperation (MLC) involvement radical intermediates during

Language: Английский

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Nickel Pincer Complexes Catalyzed Sustainable Synthesis of 3,4-Dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxides via Acceptorless Dehydrogenative Coupling of Primary Alcohols

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2494 - 2504

Published: Feb. 7, 2024

We report the atom-economic and sustainable synthesis of biologically important 3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxide (DHBD) derivatives from readily available aromatic primary alcohols 2-aminobenzenesulfonamide catalyzed by nickel(II)-N∧N∧S pincer-type complexes. The synthesized nickel complexes have been well-studied elemental spectroscopic (FT-IR, NMR, HRMS) analyses. solid-state molecular structure complex 2 has authenticated a single-crystal X-ray diffraction study. Furthermore, series (24 examples) utilizing 3 mol % Ni(II) catalyst through acceptorless dehydrogenative coupling benzyl with benzenesulfonamide. Gratifyingly, catalytic protocol is highly selective yield up to 93% produces eco-friendly water/hydrogen gas as byproducts. control experiments plausible mechanistic investigations indicate that in situ generated aldehyde benzenesulfonamide leads desired product. In addition, large-scale one thiadiazine unveils synthetic usefulness current methodology.

Language: Английский

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N-Heterocyclic Carbene-Supported Nickel-Catalyzed Selective (Un)Symmetrical N-Alkylation of Aromatic Diamines with Alcohols

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(2), P. 1135 - 1146

Published: Jan. 5, 2023

The "borrowing hydrogen" (BH) approach for the N-alkylation of phenylenediamines using alcohols as coupling partners is highly challenging due to selectivity issue generated products. Furthermore, development base-metal systems that can potentially substitute precious metals with competitive activity a major challenge in BH catalysis. We present herein an efficient protocol N,N'-di-alkylation aromatic diamines situ-generated Ni-NHC complex from NiCl2 and ligand L1, which gave access wide range N,N'-di-alkylated orthophenylene (rather than generally observed benzimidazole derivatives), meta- para-phenylene along 2,6-diamino pyridine derivatives good excellent yields. Moreover, catalyst system was also successful derivatization clinically important drug molecule, Dapsone. Notably, could be applied effectively synthesize unsymmetrically substituted via sequential alkylation first report best our knowledge. Diverse control experiments including deuterium incorporation studies suggest proceeds sequence.

Language: Английский

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β‐Alkylation through Dehydrogenative Coupling of Primary Alcohols and Secondary Alcohols Catalyzed by Thioether‐Functionalized N‐Heterocyclic Carbene Ruthenium Complexes

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(23)

Published: May 24, 2023

Abstract A catalytic system for the direct β‐alkylation of secondary alcohol with primary has been investigated. In this work, a series cationic Ru(II)(η 6 ‐ p ‐cymene) complexes thioether‐functionalized N‐heterocyclic carbene ligands (imidazole‐based 1 – l and benzimidazole‐based 2 e ) have successfully synthesized evaluated as catalysts. This investigation shows that modifications in ligand moiety (thioether group and/or NHC core) strong effect on both selectivity reactivity. Imidazole‐based complex c , only mol % catalyst loading, displayed best activity well highest β‐alcohol up to 98 : tandem borrowing hydrogen/aldol methodology. Applied wide range substrates, β‐alkylated alcohols obtained moderate yields, but generally complete conversion very high selectivity.

Language: Английский

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