Switching Mechanistic Pathways by Micellar Catalysis: A Highly Selective Rhodium Catalyst for the Hydroaminomethylation of Olefins with Anilines in Water

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2702 - 2714

Published: Feb. 7, 2023

Hydroaminomethylation (HAM) is one of the most promising atom-economic processes for production secondary amines, which so far remains extremely challenging with anilines as substrates. Herein, we report use combined micellar and microwave catalysis HAM olefins in water reaction medium that allows synthesis good yields high regioselectivities. For rhodium/xantphos catalyst system, mechanistic investigations suggest a pathway different to commonly observed mechanisms homogeneous catalysts reported reaction, involving carbonylation initiated by C–H activation rather than classical hydroformylation steps.

Language: Английский

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Recent Advances in Catalytic Carbonylation Reactions in Alternative Reaction Media

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(4), P. 406 - 429

Published: Oct. 3, 2023

Comprehensive Summary Since the discovery of hydroformylation (oxo‐synthesis or Roelen reaction) and Reppe‐reaction, transition metal‐catalyzed carbonylation reactions, providing versatile, facile, even atom‐economic methods for selective incorporation C=O functionality to various skeletons, have gained tremendous importance in synthetic organic chemistry from laboratories industrial applications. The carbon‐carbon multiple bonds, aromatic halides, triflates, etc ., presence nucleophiles has led way produce aldehydes, carboxylic acids, esters, amides, fine chemical industry. However, these protocols usually proceed conventional, fossil‐based, toxic reaction environments. Thus, several attempts been directed developing efficient alternative, less harmful, non‐fossil‐based renewable media. In this review, we overview recent applications alternative solvents such as water, biomass‐based alcohols, γ‐valerolactone (GVL), 2‐methyltetrahydrofuran (2‐MeTHF), ionic liquids (ILs), deep eutectic (DES), alkyl levulinates, limonene, α‐pinene, dimethyl carbonate well fluorous media improve efficiency, safety environmentally benign nature protocols.

Language: Английский

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The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Molecules, Journal Year: 2022, Volume and Issue: 27(19), P. 6293 - 6293

Published: Sept. 23, 2022

Organophosphorus ligands are an invaluable family of compounds that continue to underpin important roles in disciplines such as coordination chemistry and catalysis. Their success can routinely be traced back facile tuneability thus enabling a high degree control over, for example, electronic steric properties. Diphosphines, phosphorus bearing two separated PIII donor atoms, also highly valued impart their own unique features, example excellent chelating properties upon metal complexation. In many classical this type, the backbone connectivity has been based on all carbon spacers only but there is growing interest embedding other atoms additional nitrogen (–NH–, –NR–) sites. This review will collate some examples field, illustrate role highlight reactivities applications. It shown incorporation nitrogen-based group unusual catalytic

Language: Английский

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A Highly Dispersed Heterogeneous Cobalt Catalyst for Efficient Domino Hydroformylation Reductive Amination of Olefins

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Abstract The hydroaminomethylation of alkenes using CO and H 2 proceeds efficiently in the presence a heterogeneous Co−N/C catalyst with highly dispersed metal centers. Various secondary tertiary amines can be effectively synthesized from cyclic linear aliphatic this specific material. active sites optimal result synergistic effect atomically Co their surrounding N atoms, high surface area as well structural defects NC support. broad applicability (>54 examples), including pharmaceutically relevant molecules, together activity reusability, underline general catalytic system.

Language: Английский

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A Highly Dispersed Heterogeneous Cobalt Catalyst for Efficient Domino Hydroformylation Reductive Amination of Olefins

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Abstract The hydroaminomethylation of alkenes using CO and H 2 proceeds efficiently in the presence a heterogeneous Co−N/C catalyst with highly dispersed metal centers. Various secondary tertiary amines can be effectively synthesized from cyclic linear aliphatic this specific material. active sites optimal result synergistic effect atomically Co their surrounding N atoms, high surface area as well structural defects NC support. broad applicability (>54 examples), including pharmaceutically relevant molecules, together activity reusability, underline general catalytic system.

Language: Английский

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Transition Metal‐Catalyzed Aminocarbonylation Reactions

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

Abstract Transition‐metal‐catalyzed aminocarbonylation reactions using low‐cost and accessible CO gas as a C1 building block amine nucleophile have been widely used to prepare amides, which are broadly exist in bioactive drugs, natural products, polymers. This type of reaction has also applied construct various biologically active heterocycles. In this review, we highlight involving under transition metal catalysis systems (palladium, rhodium, ruthenium, iridium, iron, copper, cobalt) over the past decade.

Language: Английский

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Coordination assembly enables highly selective catalytic hydroaminomethylation of olefins

Green Chemistry, Journal Year: 2022, Volume and Issue: 25(4), P. 1368 - 1379

Published: Nov. 29, 2022

The l / b selectivity in hydroaminomethylation of olefins could be boosted to 99 : 1 with 98% yield by using recyclable self-supported NHC–Rh( i ) catalysts.

Language: Английский

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Sulfonate-Modified Picolinamide Diphosphine: A Ligand for Room-Temperature Palladium-Catalyzed Hydrocarboxylation in Water with High Branched Selectivity

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12868 - 12876

Published: Sept. 19, 2023

Alkyne hydrocarboxylation represents a powerful and industrially significant approach to α,β-unsaturated carboxylic acids. Herein, we report the development of picolinamide-derived diphosphine ligand with hydrophilic sulfonate (SO3–) group. The implementation this enabled Pd-catalyzed alkynes at room temperature in water, allowing reaction proceed various substrates high yields generally excellent branched selectivity. Further experimental theoretical investigations highlight role ligand–metal cooperativity from basic pyridine accelerating key catalytic steps.

Language: Английский

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Adducts of t-butyl-substituted diphosphines with triflic acid: Synthesis, characterization and application to Pd-catalyzed methoxycarbonylation-aminolysis tandem reaction

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 429, P. 115200 - 115200

Published: Nov. 10, 2023

Language: Английский

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Recent Advances in Organic Reactions Using Water as Solvent

Published: March 8, 2024

In the past two decades, water has gradually become a green and sustainable alternative to traditional organic solvents which are generally hazardous waste productive. Due its safe, nontoxic, nonflammable, cost-effective, abundant nature, been increasingly used in various types of reactions ranging from conventional oxidation, reduction, addition, substitution, condensation, cyclization classical cross-coupling, CH activation more recent photoredox, electrochemical chemoenzymatic reactions. This chapter summarizes (2017-2022) representative examples using as solvent covers related reaction mechanisms roles that plays certain Micellar-enabled aqueous facilitated by surfactants will also be discussed.

Language: Английский

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