skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Immobilized Gold Nanoparticles Prepared from Gold(III)-Containing Ionic Liquids on Silica: Application to the Sustainable Synthesis of Propargylamines

Abstract

A cycloaurated phosphinothioic amide gold(III) complex was supported on amorphous silica with the aid of an imidazolium ionic liquid (IL) physisorbed in the SiO2 pores (SiO2–IL) and covalently bonded to the SiO2 (SiO2@IL). Gold(0) nanoparticles (AuNPs) were formed in situ and subsequently immobilized on the SiO2–IL/SiO2@IL phase. The resulting catalytic systems Au–SiO2–IL and Au–SiO2@IL promoted the solvent-free A3 coupling reaction of alkynes, aldehydes, and amines in high yields under solvent-free conditions with very low catalyst loading and without the use of additives. The Au–SiO2@IL catalyst showed good recyclability and could be reused at least five times with yields of propargylamines of ≥80%. This synthetic method provides a green and low cost way to effectively prepare propargylamines. Additionally, 31P high resolution magic angle spinning (HRMAS) NMR spectroscopy is introduced as a simple technique to establish the Au loading of the catalyst.

Authors:
ORCiD logo; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Federal Energy Management Program Office (EE-5F)
OSTI Identifier:
1482141
Grant/Contract Number:  
CTQ2014- 57157-P
Resource Type:
Published Article
Journal Name:
Molecules
Additional Journal Information:
Journal Name: Molecules Journal Volume: 23 Journal Issue: 11; Journal ID: ISSN 1420-3049
Publisher:
MDPI AG
Country of Publication:
Switzerland
Language:
English

Citation Formats

Soengas, Raquel, Navarro, Yolanda, Iglesias, María, and López-Ortiz, Fernando. Immobilized Gold Nanoparticles Prepared from Gold(III)-Containing Ionic Liquids on Silica: Application to the Sustainable Synthesis of Propargylamines. Switzerland: N. p., 2018. Web. doi:10.3390/molecules23112975.
Soengas, Raquel, Navarro, Yolanda, Iglesias, María, & López-Ortiz, Fernando. Immobilized Gold Nanoparticles Prepared from Gold(III)-Containing Ionic Liquids on Silica: Application to the Sustainable Synthesis of Propargylamines. Switzerland. doi:10.3390/molecules23112975.
Soengas, Raquel, Navarro, Yolanda, Iglesias, María, and López-Ortiz, Fernando. Wed . "Immobilized Gold Nanoparticles Prepared from Gold(III)-Containing Ionic Liquids on Silica: Application to the Sustainable Synthesis of Propargylamines". Switzerland. doi:10.3390/molecules23112975.
@article{osti_1482141,
title = {Immobilized Gold Nanoparticles Prepared from Gold(III)-Containing Ionic Liquids on Silica: Application to the Sustainable Synthesis of Propargylamines},
author = {Soengas, Raquel and Navarro, Yolanda and Iglesias, María and López-Ortiz, Fernando},
abstractNote = {A cycloaurated phosphinothioic amide gold(III) complex was supported on amorphous silica with the aid of an imidazolium ionic liquid (IL) physisorbed in the SiO2 pores (SiO2–IL) and covalently bonded to the SiO2 (SiO2@IL). Gold(0) nanoparticles (AuNPs) were formed in situ and subsequently immobilized on the SiO2–IL/SiO2@IL phase. The resulting catalytic systems Au–SiO2–IL and Au–SiO2@IL promoted the solvent-free A3 coupling reaction of alkynes, aldehydes, and amines in high yields under solvent-free conditions with very low catalyst loading and without the use of additives. The Au–SiO2@IL catalyst showed good recyclability and could be reused at least five times with yields of propargylamines of ≥80%. This synthetic method provides a green and low cost way to effectively prepare propargylamines. Additionally, 31P high resolution magic angle spinning (HRMAS) NMR spectroscopy is introduced as a simple technique to establish the Au loading of the catalyst.},
doi = {10.3390/molecules23112975},
journal = {Molecules},
number = 11,
volume = 23,
place = {Switzerland},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.3390/molecules23112975

Save / Share:

Works referenced in this record:

Single and double A3-coupling (aldehyde-amine-alkyne) reaction catalyzed by an air stable copper(I)-phosphole complex
journal, October 2017


A Simple and Efficient One-Pot Three-Component Synthesis of Propargylamines Using Bismuth (III) Chloride
journal, May 2012

  • Teimouri, Abbas; Chermahini, Alireza Najafi; Narimani, M.
  • Bulletin of the Korean Chemical Society, Vol. 33, Issue 5
  • DOI: 10.5012/bkcs.2012.33.5.1556

A 3 -Coupling catalyzed by robust Au nanoparticles covalently bonded to HS-functionalized cellulose nanocrystalline films
journal, January 2013

  • Huang, Jian-Lin; Gray, Derek G.; Li, Chao-Jun
  • Beilstein Journal of Organic Chemistry, Vol. 9
  • DOI: 10.3762/bjoc.9.155

Catalysis by gold nanoparticles: carbon-carbon coupling reactions
journal, January 2013


Eggshell Membrane-Supported Recyclable Catalytic Noble Metal Nanoparticles for Organic Reactions
journal, January 2014

  • Mallampati, Ramakrishna; Valiyaveettil, Suresh
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 4
  • DOI: 10.1021/sc4004899

Synthesis and Reactivity of Propargylamines in Organic Chemistry
journal, November 2017


Efficient Preparation of the Isoindoline Frameworkvia a Six Component, Tandem Double A3-Coupling and [2+2+2] Cycloaddition Reaction
journal, February 2008

  • Bonfield, E. Ryan; Li, Chao-Jun
  • Advanced Synthesis & Catalysis, Vol. 350, Issue 3
  • DOI: 10.1002/adsc.200700500

Recent Advances in Pd-Catalyzed Cross-Coupling Reaction in Ionic Liquids: Recent Advances in Pd-Catalyzed Cross-Coupling Reaction in Ionic Liquids
journal, February 2018

  • Li, Jianxiao; Yang, Shaorong; Wu, Wanqing
  • European Journal of Organic Chemistry, Vol. 2018, Issue 11
  • DOI: 10.1002/ejoc.201701509

Gold-Catalyzed Hydroamination of C–C Multiple Bonds
journal, October 2006

  • Widenhoefer, Ross A.; Han, Xiaoqing
  • European Journal of Organic Chemistry, Vol. 2006, Issue 20
  • DOI: 10.1002/ejoc.200600399

Combined Role of the Asymmetric Counteranion-Directed Catalysis (ACDC) and Ionic Liquid Effect for the Enantioselective Biginelli Multicomponent Reaction
journal, August 2018

  • Alvim, Haline G. O.; Pinheiro, Danielle L. J.; Carvalho-Silva, Valter H.
  • The Journal of Organic Chemistry, Vol. 83, Issue 19
  • DOI: 10.1021/acs.joc.8b02101

Triazole-gold (TAAu) catalyzed three-component coupling (A3 reaction) towards the synthesis of 2, 4-disubstituted quinoline derivatives
journal, February 2019


Direct Addition of TMS-acetylene to Aldimines Catalyzed by a Simple, Commercially Available Ir(I) Complex
journal, December 2001

  • Fischer, Christian; Carreira, Erick M.
  • Organic Letters, Vol. 3, Issue 26
  • DOI: 10.1021/ol017022q

Iron-catalyzed three-component coupling of aldehyde, alkyne, and amine under neat conditions in air
journal, June 2009


Gold and silver nanoparticles supported on metal-organic frameworks: a highly active catalyst for three-component coupling reaction
journal, May 2016

  • Liu, Lili; Tai, Xishi; Yu, Guanglin
  • Chemical Research in Chinese Universities, Vol. 32, Issue 3
  • DOI: 10.1007/s40242-016-5435-9

Interfacial Behavior of Orthoborate Ionic Liquids at Inorganic Oxide Surfaces Probed by NMR, IR, and Raman Spectroscopy
journal, July 2018

  • Shah, Faiz Ullah; Holmgren, Allan; Rutland, Mark W.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 34
  • DOI: 10.1021/acs.jpcc.8b06049

Ionic liquid and nanoparticle hybrid systems: Emerging applications
journal, June 2017


Gold(iii) stabilized over ionic liquids grafted on MCM-41 for highly efficient three-component coupling reactions
journal, January 2013

  • Bobadilla, Luis F.; Blasco, Teresa; Odriozola, José A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 39
  • DOI: 10.1039/c3cp52924j

Zn(OAc)2·2H2O: a versatile catalyst for the one-pot synthesis of propargylamines
journal, October 2007


Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts
journal, July 2006


N-Heterocyclic carbene palladium complex supported on ionic liquid-modified graphene oxide as an efficient and recyclable catalyst for Suzuki reaction
journal, January 2014

  • Movahed, Siyavash Kazemi; Esmatpoursalmani, Rahele; Bazgir, Ayoob
  • RSC Adv., Vol. 4, Issue 28
  • DOI: 10.1039/C3RA46056H

Cu(I)-catalyzed three component coupling protocol for the synthesis of quinoline derivatives
journal, September 2002


Gold nanoparticles immobilized on lipoic acid functionalized SBA-15: Synthesis, characterization and catalytic applications
journal, March 2013


Imidazolium-based ionic liquids grafted on solid surfaces
journal, January 2014


Highly efficient three-component coupling reaction catalyzed by gold nanoparticles supported on periodic mesoporous organosilica with ionic liquid framework
journal, January 2012

  • Karimi, Babak; Gholinejad, Mohammad; Khorasani, Mojtaba
  • Chemical Communications, Vol. 48, Issue 71
  • DOI: 10.1039/c2cc33320a

Immobilization of Pd(OAc) 2 in Ionic Liquid on Silica:  Application to Sustainable Mizoroki−Heck Reaction
journal, July 2004

  • Hagiwara, Hisahiro; Sugawara, Yoshitaka; Isobe, Kohei
  • Organic Letters, Vol. 6, Issue 14
  • DOI: 10.1021/ol049343i

The silver salt of 12-tungstophosphoric acid: an efficient catalyst for the three-component coupling of an aldehyde, an amine and an alkyne
journal, October 2006


Ionic Liquids in Asymmetric Synthesis: An Overall View from Reaction Media to Supported Ionic Liquid Catalysis
journal, June 2018


A Review on Recent Advances in the Application of Nanocatalysts in A 3 Coupling Reactions
journal, March 2018

  • Nasrollahzadeh, Mahmoud; Sajjadi, Mohaddeseh; Ghorbannezhad, Fatemeh
  • The Chemical Record, Vol. 18, Issue 10
  • DOI: 10.1002/tcr.201700100

New protocols to access imidazoles and their ring fused analogues: synthesis from N-propargylamines
journal, January 2017

  • Vessally, Esmail; Soleimani-Amiri, Somayeh; Hosseinian, Akram
  • RSC Advances, Vol. 7, Issue 12
  • DOI: 10.1039/C6RA25816F

InBr3-catalyzed three-component reaction: a facile synthesis of propargyl amines
journal, July 2009


Efficient one-pot synthesis of propargylamines catalysed by gold nanocrystals stabilized on montmorillonite
journal, January 2014

  • Borah, Bibek Jyoti; Borah, Subrat Jyoti; Saikia, Kokil
  • Catal. Sci. Technol., Vol. 4, Issue 11
  • DOI: 10.1039/C4CY00666F

Mercurous Chloride Catalyzed Mannich Condensation of Terminal Alkynes with Secondary Amines and Aldehydes
journal, August 2005


Reactions of secondary propargylamines with heteroallenes for the synthesis of diverse heterocycles
journal, January 2018

  • Peshkov, Vsevolod A.; Pereshivko, Olga P.; Nechaev, Anton A.
  • Chemical Society Reviews, Vol. 47, Issue 11
  • DOI: 10.1039/C7CS00065K

Organonitrile ligated silver complexes with perfluorinated weakly coordinating anions and their catalytic application for coupling reactions
journal, January 2005

  • Zhang, Yanmei; Santos, Ana M.; Herdtweck, Eberhardt
  • New J. Chem., Vol. 29, Issue 2
  • DOI: 10.1039/B414060E

Three-component coupling of aldehyde, alkyne, and amine catalyzed by silver in ionic liquid
journal, March 2004


Highly efficient Grignard-type imine additions via C–H activation in water and under solvent-free conditions
journal, January 2002

  • Li, Chao-Jun; Wei, Chunmei
  • Chemical Communications, Issue 3
  • DOI: 10.1039/b108851n

Alkynylation of N-tosylimines with aryl acetylenes promoted by ZnBr2 and N,N-diisopropylethylamine in acetonitrile
journal, January 2005


A Highly Efficient Three-Component Coupling of Aldehyde, Alkyne, and Amines via C−H Activation Catalyzed by Gold in Water
journal, August 2003

  • Wei, Chunmei; Li, Chao-Jun
  • Journal of the American Chemical Society, Vol. 125, Issue 32
  • DOI: 10.1021/ja0359299

The First Cobalt-Catalyzed Transformation of Alkynyl C-H Bond: Aldehyde-Alkyne-Amine (A³) Coupling
journal, January 2010


Progress in Synthesis of Propargylamine and Its Derivatives by Nanoparticle Catalysis via A3 coupling: A Decade Update
journal, January 2018


Attempts to Fill the Gap Between Enzymatic, Homogeneous, and Heterogeneous Catalysis
journal, December 2004


Factors Influencing the Activity, Selectivity, and Stability of Rh-Based Supported Ionic Liquid Phase (SILP) Catalysts for Hydroformylation of Propene
journal, February 2012

  • Shylesh, Sankaranarayanapillai; Hanna, David; Werner, Sebastian
  • ACS Catalysis, Vol. 2, Issue 4
  • DOI: 10.1021/cs2004888

New Page to Access Pyrazines and their Ring Fused Analogues: Synthesis from N-Propargylamines
journal, April 2017


Microwave-Promoted Three-Component Coupling of Aldehyde, Alkyne, and Amine via C−H Activation Catalyzed by Copper in Water
journal, March 2004

  • Shi, Lei; Tu, Yong-Qiang; Wang, Min
  • Organic Letters, Vol. 6, Issue 6
  • DOI: 10.1021/ol049936t

Efficient one-pot synthesis of propargylamines using zinc dust
journal, October 2007


Some insights into the gold-catalysed A 3 -coupling reaction
journal, October 2017


Layered Double Hydroxide-Supported Gold Catalyst for Three-Component Aldehyde-Amine-Alkyne Coupling
journal, January 2005


Cooperative catalysis by acid–base bifunctional graphene
journal, January 2013

  • Li, Yang; Zhao, Qingshan; Ji, Junyi
  • RSC Advances, Vol. 3, Issue 33
  • DOI: 10.1039/c3ra41970c

Gold immobilized onto poly(ionic liquid) functionalized magnetic nanoparticles: a robust magnetically recoverable catalyst for the synthesis of propargylamine in water
journal, January 2015

  • Moghaddam, Firouz Matloubi; Ayati, Seyed Ebrahim; Hosseini, Seyed Hassan
  • RSC Advances, Vol. 5, Issue 43
  • DOI: 10.1039/C5RA02974K

A walk around the A3-coupling
journal, January 2012

  • Peshkov, Vsevolod A.; Pereshivko, Olga P.; Van der Eycken, Erik V.
  • Chemical Society Reviews, Vol. 41, Issue 10
  • DOI: 10.1039/c2cs15356d

Copper nanoparticles stabilized on nitrogen-doped carbon nanotubes as efficient and recyclable catalysts for alkyne/aldehyde/cyclic amine A3-type coupling reactions
journal, July 2012

  • Ramu, Vasanthakumar Ganga; Bordoloi, Ankur; Nagaiah, Tharamani C.
  • Applied Catalysis A: General, Vol. 431-432
  • DOI: 10.1016/j.apcata.2012.04.019

Development of gold nanoparticle-fungal hybrid based heterogeneous interface for catalytic applications
journal, August 2015


Preparation of Tremorine and Gemini Surfactant Precursors with Cationic Ethynyl-Bridged Digold Catalysts
journal, February 2017

  • Grirrane, Abdessamad; Álvarez, Eleuterio; García, Hermenegildo
  • Chemistry - A European Journal, Vol. 23, Issue 12
  • DOI: 10.1002/chem.201605269

Transition Metal-Catalysed, Direct and Site-Selective N1-, C2- or C3-Arylation of the Indole Nucleus: 20 Years of Improvements
journal, March 2009

  • Joucla, Lionel; Djakovitch, Laurent
  • Advanced Synthesis & Catalysis, Vol. 351, Issue 5
  • DOI: 10.1002/adsc.200900059

Indium-Catalyzed Highly Efficient Three-Component Coupling of Aldehyde, Alkyne, and Amine via C−H Bond Activation
journal, June 2009

  • Zhang, Yicheng; Li, Pinhua; Wang, Min
  • The Journal of Organic Chemistry, Vol. 74, Issue 11
  • DOI: 10.1021/jo900507v

Gold(III) Salen Complex-Catalyzed Synthesis of Propargylamines via a Three-Component Coupling Reaction
journal, April 2006

  • Lo, Vanessa Kar-Yan; Liu, Yungen; Wong, Man-Kin
  • Organic Letters, Vol. 8, Issue 8
  • DOI: 10.1021/ol0528641

When Gold Is Not Noble: Catalysis by Nanoparticles
journal, April 2003


Recent Advances in Catalytic Condensation Reactions Applications of Supported Ionic Liquids
journal, May 2018


Direct Synthesis of 2-(Aminomethyl)indoles through Copper(I)-Catalyzed Domino Three-Component Coupling and Cyclization Reactions
journal, March 2007

  • Ohno, Hiroaki; Ohta, Yusuke; Oishi, Shinya
  • Angewandte Chemie International Edition, Vol. 46, Issue 13
  • DOI: 10.1002/anie.200604342

A Gold-Catalyzed A3 Coupling/Cyclization/Elimination Sequence as Versatile Tool for the Synthesis of Furfuryl Alcohol Derivatives from Glyceraldehyde and Alkynes
journal, January 2016

  • Li, Jian; Rudolph, Matthias; Rominger, Frank
  • Advanced Synthesis & Catalysis, Vol. 358, Issue 2
  • DOI: 10.1002/adsc.201500812

Catalysis by Supported Gold Nanoparticles: Beyond Aerobic Oxidative Processes
journal, May 2012

  • Stratakis, Manolis; Garcia, Hermenegildo
  • Chemical Reviews, Vol. 112, Issue 8
  • DOI: 10.1021/cr3000785

Efficient Synthesis of Propargylamines in Aqueous Media Catalyzed by Au Nanoparticles under Ambient Temperature
journal, February 2018


The First Silver-Catalyzed Three-Component Coupling of Aldehyde, Alkyne, and Amine
journal, November 2003

  • Wei, Chunmei; Li, Zigang; Li, Chao-Jun
  • Organic Letters, Vol. 5, Issue 23
  • DOI: 10.1021/ol035781y

Supported Gold(III) Catalysts for Highly Efficient Three-Component Coupling Reactions
journal, May 2008

  • Zhang, Xin; Corma, Avelino
  • Angewandte Chemie International Edition, Vol. 47, Issue 23
  • DOI: 10.1002/anie.200800098

The effect of counteranion on the physicochemical and thermal properties of 4-methyl-1-propyl-1,2,4-triazolium ionic liquids
journal, October 2015


Supported Ionic Liquid Catalysis − A New Concept for Homogeneous Hydroformylation Catalysis
journal, November 2002

  • Mehnert, Christian P.; Cook, Raymond A.; Dispenziere, Nicholas C.
  • Journal of the American Chemical Society, Vol. 124, Issue 44
  • DOI: 10.1021/ja0279242

Heterogenized Gold Complexes: Recoverable Catalysts for Multicomponent Reactions of Aldehydes, Terminal Alkynes, and Amines
journal, February 2012

  • Villaverde, Gonzalo; Corma, Avelino; Iglesias, Marta
  • ACS Catalysis, Vol. 2, Issue 3
  • DOI: 10.1021/cs200601w

Aldehyde–alkyne–amine (A 3 ) coupling catalyzed by a highly efficient dicopper complex
journal, January 2015

  • Chen, Hong-Bin; Zhao, Yan; Liao, Yi
  • RSC Advances, Vol. 5, Issue 47
  • DOI: 10.1039/C5RA04729C

N- Propargylamines: versatile building blocks in the construction of thiazole cores
journal, January 2017

  • Arshadi, S.; Vessally, E.; Edjlali, L.
  • Beilstein Journal of Organic Chemistry, Vol. 13
  • DOI: 10.3762/bjoc.13.61

Iron-Catalyzed Ligand-Free Three-Component Coupling Reactions of Aldehydes, Terminal Alkynes, and Amines
journal, February 2009

  • Li, Pinhua; Zhang, Yicheng; Wang, Lei
  • Chemistry - A European Journal, Vol. 15, Issue 9
  • DOI: 10.1002/chem.200802643

Gold Nanoparticles-Decorated Dithiocarbamate Nanocomposite: An Efficient Heterogeneous Catalyst for the Green A3-Coupling Synthesis of Propargylamines
journal, September 2018


Ionic liquids in biotechnology and beyond
journal, January 2018


14N NMR and Two-Dimensional Suspension1H and13C HRMAS NMR Spectroscopy of Ionic Liquids Immobilized on Silica
journal, March 2006

  • Brenna, Stefano; Posset, Tobias; Furrer, Julien
  • Chemistry - A European Journal, Vol. 12, Issue 10
  • DOI: 10.1002/chem.200501193

Supported Au/MIL-53(Al): a reusable green solid catalyst for the three-component coupling reaction of aldehyde, alkyne, and amine
journal, April 2016

  • Liu, Lili; Tai, Xishi; Zhang, Nana
  • Reaction Kinetics, Mechanisms and Catalysis, Vol. 119, Issue 1
  • DOI: 10.1007/s11144-016-1034-5