An Efficient Synthesis of Propargylamines via C—H Activation Catalyzed by Copper(I) in Ionic Liquids.

Park, Soon Bong; Alper, Howard

doi:10.1002/chin.200531066

Cited by 119 publications

(6 citation statements)

References 2 publications

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“…Independently, we found that the three-component addition of aldehyde, alkyne, and secondary amines can be catalyzed by CuI under solventless conditions with microwave irradiation . Alper showed that such a reaction is highly effective in ionic liquids . Formaldehyde as substrate for CuI-catalyzed A 3 coupling in aqueous solution has been reported recently.…”

Section: Addition Of Terminal Alkyne To Imine Tosylimine Iminium Ion ...mentioning

confidence: 87%

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

2010

Acc. Chem. Res.

359

100

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One of the major research endeavors in synthetic chemistry over the past two decades is the exploration of synthetic methods that work under ambient atmosphere with benign solvents, that maximize atom utilization, and that directly transform natural resources, such as renewable biomass, from their native states into useful chemical products, thus avoiding the need for protecting groups. The nucleophilic addition of terminal alkynes to various unsaturated electrophiles is a classical (textbook) reaction in organic chemistry, allowing the formation of a C-C bond while simultaneously introducing the alkyne functionality. A prerequisite of this classical reaction is the stoichiometric generation of highly reactive metal acetylides. Over the past decade, our laboratory and others have been exploring an alternative, the catalytic and direct nucleophilic addition of terminal alkynes to unsaturated electrophiles in water. We found that various terminal alkynes can react efficiently with a wide range of such electrophiles in water (or organic solvent) in the presence of simple and readily available catalysts, such as copper, silver, gold, iron, palladium, and others. In this Account, we describe the development of these synthetic methods, focusing primarily on results from our laboratory. Our studies include the following: (i) catalytic reaction of terminal alkynes with acid chloride, (ii) catalytic addition of terminal alkynes to aldehydes and ketones, (iii) catalytic addition of alkynes to C=N bonds, and (iv) catalytic conjugate additions. Most importantly, these reactions can tolerate various functional groups and, in many cases, perform better in water than in organic solvents, clearly defying classical reactivities predicated on the relative acidities of water, alcohols, and terminal alkynes. We further discuss multicomponent and enantioselective reactions that were developed. These methods provide an alternative to the traditional requirement of separate steps in classical alkyne reactions, including the pregeneration of metal acetylides with stoichiometric, highly basic reagents and the preprotection of sensitive functional groups. Accordingly, these techniques have greatly enhanced overall synthetic efficiencies and furthered our long-term objective of developing Grignard-type reactions in water.

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Section: Addition Of Terminal Alkyne To Imine Tosylimine Iminium Ion ...mentioning

confidence: 87%

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

2010

Acc. Chem. Res.

359

100

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“…However, during the course of the reaction, most of these catalytic systems suffer from a loss of the costly or hazardous catalysts. In order to achieve recyclable catalysts, Ag(I) and Cu(I) in ionic liquids have been developed by Li et al 29 and Park et al, 37 respectively. Kidwai et al 38 reported gold nanoparticles as reusable catalysts, and Corma et al 39 developed CeO 2 and ZrO 2 -stabilized Au(III) as efficient catalysts for A3 coupling reactions.…”

Section: ■ Introductionmentioning

confidence: 99%

Polyacrylonitrile Fiber Supported N-Heterocyclic Carbene Ag(I) As Efficient Catalysts for Three-Component Coupling and Intramolecular 1,3-Dipolar Cycloaddition Reactions under Flow Conditions

Cao

et al. 2017

ACS Sustainable Chem. Eng.

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A series of recoverable and reusable N-heterocyclic carbene silver complexes supported on polyacrylonitrile fiber were prepared and characterized. Their catalytic performances in three-component coupling reactions of aldehydes, amines, and alkynes (A3 coupling) to synthesize propargylamines were evaluated. The catalysts were also used to prepare fused triazoles in one-pot reactions with excellent yields and diastereoselectivities. In these reactions, the substrates underwent A3 coupling followed by intramolecular 1,3-dipolar cycloaddition. The above reactions were also successfully performed in a continuous-flow process, and sustainable, modular, and efficient syntheses of propargylamines and fused triazoles were achieved.

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“…Ultrasound can also be used for such reactions in water [118]. Such a reaction was shown by Alper et al in ionic liquids [119].…”

Section: Catalytic Nucleophilic Additions Via Ch Reactionmentioning

confidence: 95%

Unorthodox chemistry for an unorthodox challenge: Exploration of new chemical reactivities for a sustainable future

2011

Sci. China Chem.

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The sustainable development of our future represents an unorthodox challenge in sciences and technologies. The exploration of unconventional chemical reactivities that could potentially result in more sustainable chemical productions with efficient utilization of resource and inherent prevention of waste will provide the foundation for the synthetic chemistry of our future. As part of this endeavor, we have explored metal-mediated reactions in water to minimize protection-deprotection and the use of organic solvents, catalytic nucleophilic additions via C-H reactions to avoid generation and use of stoichiometric organic halides and metal in water, and Cross-Dehydrogenative-Coupling (CDC) reactions to minimize overall transformation steps. green chemistry, organometallic reactions in water, aldehyde-alkyne-amine coupling, cross-dehydrogenative-coupling

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An Efficient Synthesis of Propargylamines via C—H Activation Catalyzed by Copper(I) in Ionic Liquids.

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 119 publications

References 2 publications

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

The Development of Catalytic Nucleophilic Additions of Terminal Alkynes in Water

Polyacrylonitrile Fiber Supported N-Heterocyclic Carbene Ag(I) As Efficient Catalysts for Three-Component Coupling and Intramolecular 1,3-Dipolar Cycloaddition Reactions under Flow Conditions

Unorthodox chemistry for an unorthodox challenge: Exploration of new chemical reactivities for a sustainable future

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