Skip to main content
SpringerLink
Log in

Practical synthesis of silyl-protected and functionalized propargylamines using nanostructured Ag/TiO2 and Pt/TiO2 as active recyclable catalysts

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Herein we report the use of Ag/TiO2 and Pt/TiO2 nanocatalysts to promote the synthesis of a series of silyl-protected and functionalized propargylamine derivatives through alkyne–amine–aldehyde (A3) coupling under microwave condition using water as solvent in short reaction times with high yielding production. A comparative study between the two catalysts was also demonstrated to prove that Pt/TiO2 nanocomposite has higher potential effect for propargylamines synthesis more than Ag/TiO2. The main features of the investigated method for propargylamines synthesis were easy handling, low catalyst loading as well as the feasibility of catalyst recyclability. The prepared compounds are potentially beneficial with possible pharmacological and biological properties, which that could be used in several disciplines including medicinal and agricultural applications.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Scheme 1
Scheme 2
Fig. 4
Fig. 5
Fig. 6
Scheme 3
Scheme 4

Similar content being viewed by others

References

  • Abbiati G, Rossi E (2014) Silver and gold-catalyzed multicomponent reactions. Beilstein J Org Chem 10:481–513

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Aguilar D, Contel M, Urriolabeitia EP (2010) Mechanistic insights into the one-pot synthesis of propargylamines from terminal alkynes and amines in chlorinated solvents catalyzed by gold compounds and nanoparticles. Chem Eur J 16(30):9287–9296

    Article  CAS  PubMed  Google Scholar 

  • Al-Qaisi JA, Alhussainy TM, Qinna NA, Matalka KZ, Al-Kaissi EN, Muhi-Eldeen ZA (2014) Synthesis and pharmacological evaluation of aminoacetylenic isoindoline-1,3-dione derivatives as anti-inflammatory agents. Arab J Chem 7(6):1024–1030

    Article  CAS  Google Scholar 

  • Attia YA, Vázquez CV, Mohamed YMA (2017) Facile production of vitamin B3 and other heterocyclic carboxylic acids using an efficient Ag/ZnO/graphene-Si hybrid nanocatalyst. Res Chem Intermed 43(1):203–218

    Article  CAS  Google Scholar 

  • Bagheri S, Julkapli NM, Abd Hamid SB (2014) Titanium dioxide as a catalyst support in heterogeneous catalysis. Sci World J 2014:727496

    Article  CAS  Google Scholar 

  • Bellardita M, El Nazer HA, Loddo V, Parrino F, Venezia AM, Palmisano L (2017) Photoactivity under visible light of metal loaded TiO2 catalysts prepared by low frequency ultrasound treatment. Catal Today 284:92–99

    Article  CAS  Google Scholar 

  • Bieber LW, Da Silva MF (2004) Mild and efficient synthesis of propargylamines by copper-catalyzed Mannich reaction. Tetrahedron Lett 45(45):8281–8283

    Article  CAS  Google Scholar 

  • Borah SJ, Das DK (2016) Modified Montmorillonite clay stabilized silver nanoparticles: an active heterogeneous catalytic system for the synthesis of propargylamines. Catal Lett 146(3):656–665

    Article  CAS  Google Scholar 

  • Borah BJ, Borah SJ, Saikia K, Dutta DK (2014) Efficient one-pot synthesis of propargylamines catalysed by gold nanocrystals stabilized on montmorillonite. Catal Sci Technol 4:4001–4009

    Article  CAS  Google Scholar 

  • Cardoso FSP, Abboud K, Aponick A (2013) Design, preparation, and implementation of an imidazole-based chiral biaryl P, N-ligand for asymmetric Catalysis. J Am Chem Soc 135(39):14548–14551

    Article  CAS  PubMed  Google Scholar 

  • Fischer C, Carreira EM (2004) MgI2 as an additive in Ir(I)-catalyzed addition of silylacetylenes to imines: expeditious synthesis of propargylic amines. Synthesis 9:1497–1503

    Google Scholar 

  • Gao J, Song Q-W, He L-N, Yang Z-Z, Dou X-Y (2012) Efficient iron(III)-catalyzed three-component coupling reaction of alkynes, CH2Cl2 and amines to propargylamines. Chem Commun 48(14):2024–2026

    Article  CAS  Google Scholar 

  • GhavamiNejad A, Kalantarifard A, Yang GS, Kim CS (2016) In-situ immobilization of silver nanoparticles on ZSM-5 type zeolite by catechol redox chemistry, a green catalyst for A3-coupling reaction. Microporous Mesoporous Mater 225:296–302

    Article  CAS  Google Scholar 

  • Gommermann N, Koradin C, Polborn K, Knochel P (2003) Enantioselective, copper(I)-catalyzed three-component reaction for the preparation of propargylamines. Angew Chem Int Ed 42(46):5763–5766

    Article  CAS  Google Scholar 

  • Haji M (2016) Multicomponent reactions: a simple and efficient route to heterocyclic phosphonates. Beilstein J Org Chem 12:1269–1301

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Jeon H-B, Lee Y, Qiao C, Huang H, Sayre LM (2003) Inhibition of bovine plasma amine oxidase by 1,4-diamino-2-butenes and -2-butynes. Bioorg Med Chem 11(21):4631–4641

    Article  CAS  PubMed  Google Scholar 

  • Jokubaityte S et al (1980) Synthesis and properties of acetylene derivatives from phenoxypropargyl. Lietuvos TSR Mokslu Akademijos Darbai Serija B: Chemija Technika, Fizine Geografija 1:35–42

    Google Scholar 

  • Kano T, Kobayashi R, Maruoka K (2016) Synthesis of N-Boc-propargylic and allylic Amines by reaction of organomagnesium reagents with N-Boc-aminals and their oxidation to N-Boc-ketimines. Org Lett 18(2):276–279

    Article  CAS  PubMed  Google Scholar 

  • Kashid VS, Balakrishna MS (2018) Microwave-assisted copper(I) catalyzed A3-coupling reaction: reactivity, substrate scope and the structural characterization of two coupling products. Catal Commun 103:78–82

    Article  CAS  Google Scholar 

  • Li Z, Li C-J (2004) CuBr-catalyzed efficient alkynylation of sp3 C–H bonds adjacent to a nitrogen Atom. J Am Chem Soc 126(38):11810–11811

    Article  CAS  PubMed  Google Scholar 

  • Lo VK-Y, Liu Y, Wong M-K, Che C-M (2006) Gold(III) Salen complex-catalyzed synthesis of propargylamines via a three-component coupling reaction. Org Lett 8(8):1529–1532

    Article  CAS  PubMed  Google Scholar 

  • Loukopoulos E, Kallitsakis M, Tsoureas N, Abdul-Sada A, Chilton NF, Lykakis NI, Kostakis GE (2017) Cu(II) coordination polymers as vehicles in the A3 coupling. Inorg Chem 56(9):4898–4910

    Article  CAS  PubMed  Google Scholar 

  • Lu Y, Johnstone TC, Arndtsen BA (2009) Hydrogen-bonding asymmetric metal catalysis with α-amino acids: a simple and tunable approach to high enantioinduction. J Am Chem Soc 131(32):11284–11285

    Article  CAS  PubMed  Google Scholar 

  • Menon RS, Findlay AD, Bissember AC, Banwell MG (2009) The Au(I)-catalyzed intramolecular hydroarylation of terminal alkynes under mild conditions: application to the synthesis of 2H-chromenes, coumarins, benzofurans, and dihydroquinolines. J Org Chem 74(22):8901–8903

    Article  CAS  PubMed  Google Scholar 

  • Merino P, Anoro S, Castillo E, Merchan F, Tejero T (1996) Direct vinylation and ethynylation of nitrones. stereodivergent synthesis of allyl and propargyl amines. Tetrahedron Asymmetry 7(7):1887–1890

    Article  CAS  Google Scholar 

  • Meyet CE, Pierce CJ, Larsen CH (2012) A single Cu(II) catalyst for the three-component coupling of diverse nitrogen sources with aldehydes and alkynes. Org Lett 14(4):964–967

    Article  CAS  PubMed  Google Scholar 

  • Mohamed YMA, Hansen TV (2013) Z-Stereoselective semi-reduction of alkynes: modification of the Boland protocol. Tetrahedron 69(19):3872–3877

    Article  CAS  Google Scholar 

  • Mohamed YMA, Solum EJ (2017) An efficient stereoselective synthesis of a sulfur-bridged analogue of bosseopentaenoic acid as a potential antioxidant agent. Arkivoc 2017:10–19

    Article  Google Scholar 

  • Nguyen LHT, Nguyen T, Nguyen L, Doan TLH, Tran PH (2017) A new superacid hafnium-based metal-organic framework as a highly active heterogeneous catalyst for the synthesis of benzoxazoles under solvent-free conditions. Catal Sci Technol 7(19):4346–4350

    Article  CAS  Google Scholar 

  • Oi EL, Choo M-Y, Lee HV, Ong HC, Abd Hamid SB, Juan JC (2016) Recent advances of titanium dioxide (TiO2) for green organic synthesis. RSC Adv 6(110):108741–108754

    Article  CAS  Google Scholar 

  • Okamura T, Asano K, Matsubara S (2010) Effects of a flexible alkyl chain on an imidazole ligand for copper-catalyzed mannich reactions of terminal alkynes. Synlett 20:3053–3056

    Google Scholar 

  • Oldfield V, Keating GM, Perry CM (2007) Rasagiline a review of its use in the management of Parkinson’s disease. Drugs 67(12):1725–1747

    Article  CAS  PubMed  Google Scholar 

  • Panagiotopoulou P, Karamerou EE, Kondarides DI (2013) Kinetics and mechanism of glycerol photo-oxidation and photo-reforming reactions in aqueous TiO2 and Pt/TiO2 suspensions. Catal Today 209:91–98

    Article  CAS  Google Scholar 

  • Petroff JT, Nguyen AH, Porter AJ, Morales FD, Kennedy MP, Weinstein D, El Nazer H, McCulla RD (2017) Enhanced photocatalytic dehalogenation of aryl halides by combined poly-p-phenylene (PPP) and TiO2 photocatalysts. J Photochem Photobiol A 335:149–154

    Article  CAS  Google Scholar 

  • Qi R, Wang X-N, DeKorver KA, Tang Y, Wang C-C, Li Q, Li H, Lv M-C, Rodriques KE, Basha A, Summers JB, Brooks DW (1988) Addition of aryllithium compounds to oxime ethers. Tetrahedron Lett 29(28):3455–3458

    Article  Google Scholar 

  • Riederer P, Lachenmayer L (2003) Selegiline’s neuroprotective capacity revisited. J Neural Transmission 110(11):1273–1278

    Article  CAS  Google Scholar 

  • Sakai N, Kanada R, Hirasawa M, Konakahara T (2005) Facile and convenient synthesis of functionalized propargylic alcohols and amines: an InBr 3-Et3 N reagent system promotes the alkynylation of aldehydes and N, O- or N, S-acetals. Tetrahedron 61(39):9298–9304

    Article  CAS  Google Scholar 

  • Sarode PB, Bahekar SP, Chandak HS (2016) Zn(OTf)2-mediated expeditious and solvent-Free synthesis of propargylamines via C–H activation of phenylacetylene. Synlett 27(15):2209–2212

    Article  CAS  Google Scholar 

  • Schmickler W, Santos E (2010) Interfacial electrochemistry, 2nd edn. Springer-Verlag, Berlin Heidelberg, pp 9–18

    Book  Google Scholar 

  • Shah AP, Sharma AS, Jain S, Shimpi NG (2018) Microwave assisted one pot three component synthesis of propargylamine, tetra substituted propargylamine and pyrrolo[1,2-a]quinolines using CuNPs@ZnO–PTh as a heterogeneous catalyst. New J Chem 42:8724–8737

    Article  CAS  Google Scholar 

  • Sharma N, Sharma UK, Mishra NM, Van der Eyckena EV (2014) Copper-catalyzed diversity-oriented three- and five-component synthesis of mono- and dipropargylic amines via coupling of alkynes, α-amino esters and aldehydes. Adv Synth Catal 356(5):1029–1037

    Article  CAS  Google Scholar 

  • Shi J, Ai H, Chen J, Cui H, Yang S, Li S, Fu M (2014) Nitrogen doped titania plates with dominant 0 0 1 facets: microstructure and property evolution, and their photocatalytic activities. J Mol Catal A 395:420–427

    Article  CAS  Google Scholar 

  • Trivedi M, Singh G (2015) Silver(I) complexes as efficient source for silver oxide nanoparticles with catalytic activity in A3 coupling reactions. Inorg Chim Acta 438:255–263

    Article  CAS  Google Scholar 

  • Vessally E, Hosseinian A, Edjlali L, Bekhradnia A, Esrafili MD (2016) New route to 1,4-oxazepane and 1,4-diazepane derivatives: synthesis from N-propargylamines. RSC Adv 6(102):99781–99793

    Article  CAS  Google Scholar 

  • Wei C, Li Z, Li C-J (2003) The first silver-catalyzed three-component coupling of aldehyde, alkyne, and amine. Org Lett 5(23):4473–4475

    Article  CAS  PubMed  Google Scholar 

  • Wender PA (2014) Toward the ideal synthesis and molecular function through synthesis-informed design. Nat Prod Rep 31(4):433–440

    Article  CAS  PubMed  Google Scholar 

  • Xu X, Li X (2009) Copper/Diethyl azodicarboxylate mediated regioselective alkynylation of unactivated aliphatic tertiary methylamine with terminal alkyne. Org Lett 11(4):1027–1029

    Article  CAS  PubMed  Google Scholar 

  • Xu Z, Yu X, Feng X, Bao M (2011) Propargylamine synthesis by copper-catalyzed oxidative coupling of alkynes and tertiary amine N-oxides. J Org Chem 76(16):6901–6905

    Article  CAS  PubMed  Google Scholar 

  • Yi WT, Yan CY, Yan P, Li FQ (2014) A new perspective for effect of S and Cu on the photocatalytic activity of S, Cu-codoped nano-TiO2 under visible light irradiation. J Sol-gel Sci Technol 69(2):386–396

    Article  CAS  Google Scholar 

  • Zani L, Alesi S, Cozzi PG, Bolm C (2006) Dimethylzinc-mediated alkynylation of imines. J Org Chem 71(4):1558–1562

    Article  CAS  PubMed  Google Scholar 

  • Zhang H, Zhang P, Jiang M, Yang H, Fu H (2017) Merging photoredox with copper catalysis: decarboxylative alkynylation of α-amino acid derivatives. Org Lett 19(5):1016–1019

    Article  CAS  PubMed  Google Scholar 

  • Zhao C, Seidel D (2015) Enantioselective A3 reactions of secondary amines with a Cu(I)/acid-thiourea catalyst combination. J Am Chem Soc 137(14):4650–4653

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors are grateful to the National Research Center (Egypt) and NORD University (Norway) for providing the facilities.

Author information

Authors and Affiliations

  1. Photochemistry Department, National Research Center, Dokki, Giza, 12622, Egypt

    Yasser M. A. Mohamed & Hossam A. El Nazer

  2. Faculty of Health Sciences, NORD University, 7800, Namsos, Norway

    Eirik Johansson Solum

Authors
  1. Yasser M. A. Mohamed
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hossam A. El Nazer
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Eirik Johansson Solum
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Yasser M. A. Mohamed or Hossam A. El Nazer.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mohamed, Y.M.A., El Nazer, H.A. & Solum, E.J. Practical synthesis of silyl-protected and functionalized propargylamines using nanostructured Ag/TiO2 and Pt/TiO2 as active recyclable catalysts. Chem. Pap. 73, 435–445 (2019). https://doi.org/10.1007/s11696-018-0604-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11696-018-0604-6

Keywords

Search

Navigation