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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Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13451 - 13496

Published: Aug. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Language: Английский

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

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

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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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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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Microwave-assisted pincer-ruthenium catalyzed Guerbet reaction for the upgradation of bio-ethanol to bio-butanol

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(6), P. 1763 - 1776

Published: Jan. 1, 2023

Bis(benzimidazole-2-yl)pyridine based pincer-ruthenium (immobilized or otherwise) catalyzes the upgradation of feed agnostic bio-ethanol to fuel grade n -butanol at unprecedented turnovers under microwave conditions within two hours reaction.

Language: Английский

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Highly Efficient Base Catalyzed N‐alkylation of Amines with Alcohols and β‐Alkylation of Secondary Alcohols with Primary Alcohols

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(20)

Published: Aug. 8, 2023

Abstract Borrowing hydrogen (BH) reactions are very useful for the sustainable synthesis of C−C and C−N bonds. They generally operate with transition metal‐based catalysts along stoichiometric/catalytic amounts added base. Here we report that two catalytic transformations, carried out BH methodology, i. e. N ‐alkylation amines alcohols β‐alkylation secondary primary alcohols, can be performed effectively just base under air without using any catalyst. The mechanism is proposed to based on oxidation alcohol aldehyde followed by condensation an unsaturated intermediate which undergoes transfer hydrogenation product.

Language: Английский

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Selective cross-coupling of α,β-unsaturated nitriles with aldehydes or alcohols by hydrogen transfer catalysis towards β-ketonitriles and glutaronitriles

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2613 - 2623

Published: Jan. 1, 2024

A Ru-catalyzed selective hydroacylation of acrylonitriles with aldehydes or alcohols towards β-ketonitriles is established. Glutaronitriles can be obtained through a one-step tandem and Michael addition acrylonitrile alcohols.

Language: Английский

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Temperature-dependent switchable synthesis of imines and amines via coupling of alcohols and amines using pyrrolyl-imine ruthenium catalysts

Journal of Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 115895 - 115895

Published: Dec. 1, 2024

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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