SpringerLink
Log in

Cyclohexyl iodide promoted approach for coumarin analog synthesis using small scaffold

  • Full-Length Paper
  • Published:
Molecular Diversity Aims and scope Submit manuscript

Abstract

New chemical approaches were adopted for the synthesis of biologically important coumarins utilizing cyclohexane-1,3-dione derivatives as novel scaffold which were prepared from acetone and ethyl acrylate following our previous report. The stepwise strategies of aromatization, dehydrogenation, and demethylative cyclization were followed for coumarins synthesis from cyclohexane-1,3-dione derivatives. This work reports the first time cyclohexyl iodide was used for the demethylative cyclization reaction of \(\upbeta , \upbeta \)-diaryl acrylates for 4-arylcoumarins synthesis.

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

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Lacy A, O’Kennedy R (2004) Studies on coumarins and coumarin-related compounds to determine their therapeutic role in the treatment of cancer. Curr Pharm Des 10:3797–3811. doi:10.2174/1381612043382693

    Article  PubMed  CAS  Google Scholar 

  2. Borges F, Roleira F, Milhazes N, Santana L, Uriarte E (2005) Simple coumarins and analogues in medicinal chemistry: occurrence, synthesis and biological activity. Curr Med Chem 12:887–916. doi:10.2174/0929867053507315

    Article  PubMed  CAS  Google Scholar 

  3. Jacquot Y, Rojaz C, Refouvelet B, Robert JF, Leclercq G, **cluna A (2003) Recent advances in the development of phytoestrogens and derivatives: an update of the promising perspectives in the prevention of postmenopausal diseases. Mini Rev Med Chem 3:387–400. doi:10.2174/1389557033488006

    Article  PubMed  CAS  Google Scholar 

  4. Rappl C, Barbier P, Bourgarel-Rey V, Gregoire C, Gilli R, Carre M, Combes S, Finet JP, Peyrot V (2006) Interaction of 4-arylcoumarin analogues of combretastatins with microtubule network of HBL100 cells and binding to tubulin. Biochemistry 45:9210–9218. doi:10.1021/bi060476g

    Article  PubMed  CAS  Google Scholar 

  5. Pierson JT, Dumetre A, Hutter S, Delmas F, Laget M, Finet JP, Azas N, Combes S (2010) Synthesis and antiprotozoal activity of 4-arylcoumarins. Eur J Med Chem 45:864–869. doi:10.1016/j.ejmech.2009.10.022

    Article  PubMed  CAS  Google Scholar 

  6. Patil AD, Freyer AJ, Eggleston DS, Haltiwanger RC, Bean MF, Taylor PB, Caranfa MJ, Breen AL, Bartus HR, Johnson RK, Hertzberg RP, Westley JW (1993) The inophyllums, novel inhibitors of HIV-1 reverse transcriptase isolated from the Malaysian tree, Calophyllum inophyllum Linn. J Med Chem 36:4131–4138. doi:10.1021/jm00078a001

    Article  PubMed  CAS  Google Scholar 

  7. Argotte-Ramos R, Ramirez-Avila G, Rodriguez-Gutierrez MC, Ovilla-Munoz M, Lanz-Mendoza H, Rodriguez MH, Gonzalez-Cortazar M, Alvarez L (2006) Antimalarial 4-phenylcoumarins from the stem bark of Hintonia latiflora. J Nat Prod 69:1442–1444. doi:10.1021/np060233p

    Article  PubMed  CAS  Google Scholar 

  8. Verotta L, Lovaglio E, Vidari G, Finzi PV, Neri MG, Raimondi A, Parapini S, Taramelli D, Riva A, Bombardelli E (2004) 4-Alkyl- and 4-phenylcoumarins from Mesua ferrea as promising multidrug resistant antibacterials. Phytochemistry 65:2867–2879. doi:10.1016/j.phytochem.2004.07.001

    Google Scholar 

  9. Wu SF, Chang FR, Wang SY, Hwang TL, Lee CL, Chen SL, Wu CC, Wu YC (2011) Anti-inflammatory and cytotoxic neoflavonoids and benzofurans from Pterocarpus santalinus. J Nat Prod 74:989–996. doi:10.1021/np100871g

    Article  PubMed  CAS  Google Scholar 

  10. Garg NK, Stoltz BM (2005) The formal total synthesis of dragmacidin B, trans-dragmacidin C, and cis-and trans-dihydrohamacanthins A. Tetrahedron Lett 46:2423–2426. doi:10.1016/j.tetlet.2005.02.054

    Article  CAS  Google Scholar 

  11. Donnelly DMX (1975) Neoflavonoids. In: Harborne JB, Mabry TJ, Mabry H (eds) The flavonoids. Academic Press, New York, pp 801–865

  12. Donnelly DMX, Finet JP, Guirya PJ, Nesbitt K (2001) Synthesis of neoflavenes by ligand coupling reactions with aryllead triacetates. Tetrahedron 57:413–423. doi:10.1016/S0040-4020(00).00955-8

    Article  CAS  Google Scholar 

  13. Chavan SP, Shivasankar K, Sivappa R, Kale R (2002) Zinc mediated transesterification of \(\beta \)-ketoesters and coumarin synthesis. Tetrahedron Lett 43:8583–8586. doi: 10.1016/S0040-4039(02)02006-3

    Article  CAS  Google Scholar 

  14. Wu J, Zhang L, **a HG (2006) Palladium-catalyzed Suzuki-Miyaura couplings of potassium aryl trifluoroborates with 4-tosyloxycoumarins or 4-tosyloxyquinolin-2(1H)-one. Tetrahedron Lett 47:1525–1528. doi:10.1016/j.tetlet.2006.01.020

    Article  CAS  Google Scholar 

  15. Park SB, Alper H (2003) Highly efficient, recyclable Pd(II) catalysts with bisimidazole ligands for the Heck reaction in ionic liquids. Org Lett 5:3209–3212. doi:10.1021/ol030071

    Article  PubMed  CAS  Google Scholar 

  16. Horaguchi T, Hosokawa N, Tanemura K, Suzuki T (2002) Photocyclization reactions. Part 8. Synthesis of 2-quinolone, quinoline and coumarin derivatives using trans–cis isomerization by photoreaction. J Heterocycl Chem 39:61–67. doi:10.1002/jhet.5570390108

    Article  CAS  Google Scholar 

  17. Dubuffet T, Luotz A, Lavielle G (1999) An efficient large scale synthesis of coumarins by a dealkylative boron-mediated ring closure of 3-(orthomethoxyaryl) propenoic esters. Synth Commun 29: 929–936. doi:10.1080/00397919908086054

    Google Scholar 

  18. Boeck F, Blazejak M, Anneser MR, Hintermann L (2012) Cyclization of ortho-hydroxycinnamates to coumarins under mild conditions: a nucleophilic organocatalysis approach. Beilstein J Org Chem 8:1630–1636. doi:10.3762/bjoc.8.186

    Article  PubMed  CAS  Google Scholar 

  19. Rao MLN, Venkatesh V, Jadhav DN (2010) Palladium-catalyzed synthesis of 4-arylcoumarins using triarylbismuth compounds as atom-efficient multicoupling organometallic nucleophiles. Eur J Org Chem 3945–3955. doi:10.1002/ejoc.201000134

  20. Sharma D, Bandna, Shil AK, Singh B, Das P (2012) Consecutive Michael-Claisen process for cyclohexane-1,3-dione derivative (CDD) synthesis from unsubstituted and substituted acetone. Synlett 23:1199–1204. doi:10.1055/s-0031-1290900

  21. Das P, Sharma D, Singh B (2011) Substituted cyclohexane-1, 3-dione compounds, process for preparation thereof and its applications. WO/2011/117881

  22. Sharma D, Bandna, Reddy CB, Kumar S, Shil AK, Guha NR, Das P (2013) Microwave assisted solvent and catalyst free method for novel classes of \(\beta \)-enaminoester and acridinedione synthesis. RSC Adv 3:10335–10340. doi:10.1039/C3RA23484C

  23. Kim JM, Lee KY, Kim JN (2003) Oxidative aromatization of 2-acylcyclohexane-1,3-dione derivatives using iodine in methanol. Bull Korean Chem Soc 24:1057–1058. doi:10.5012/bkcs.2003.24.8.1057

  24. Zuo L, Yao S, Wang W, Duan W (2008) An efficient method for demethylation of aryl methyl ethers. Tetrahedron Lett 49: 4054–4056. doi:10.1016/j.tetlet.2008.04.070

    Google Scholar 

  25. Li Y, Qi Z, Wang H, Fu X, Duan C (2012) Palladium-catalyzed oxidative Heck coupling reaction for direct synthesis of 4-arylcoumarins using coumarins and arylboronic acids. J Org Chem 77:2053–2057. doi:10.1021/jo202577m

    Article  PubMed  CAS  Google Scholar 

  26. Khoobi M, Alipour M, Zarei S, Jafarpour F, Shafiee A (2012) A facile route to flavone and neoflavone backbones via a regioselective palladium catalyzed oxidative Heck reaction. Chem Commun 48:2985–2987. doi:10.1039/C2CC18150A

    Article  CAS  Google Scholar 

  27. Das P, Sharma D, Shil AK, Kumari A (2011) Solid-supported palladium nano and microparticles: an efficient heterogeneous catalyst for ligand-free Suzuki-Miyaura cross coupling reaction. Tetrahedron Lett 52:1176–1178. doi:10.1016/j.tetlet.2011.01.009

    Article  CAS  Google Scholar 

  28. Bandna, Aggarwal N, Das P (2011) Solid-supported Pd(0): an efficient heterogeneous catalyst for aerobic oxidation of benzyl alcohols into aldehydes and ketones. Tetrahedron Lett 52:4954–4956. doi:10.1016/j.tetlet.2011.07.073

  29. Bandna, Guha NR, Shil AK, Sharma D, Das P (2012) Ligand-free solid supported palladium(0) nano/microparticles promoted C–O, C–S, and C–N cross coupling reaction. Tetrahedron Lett 53: 5318–5322. doi:10.1016/j.tetlet.2012.07.096

  30. Shil AK, Sharma D, Guha NR, Das P (2012) Solid supported Pd(0): an efficient recyclable heterogeneous catalyst for chemoselective reduction of nitroarenes. Tetrahedron Lett 53:4858–4861. doi:10.1016/j.tetlet.2012.06.132

    Article  CAS  Google Scholar 

  31. Sharma D, Kumar S, Shil AK, Guha NR, Bandna, Das P (2012) Solid supported palladium(0) nano/microparticle: a ligand-free efficient recyclable heterogeneous catalyst for mono- and \(\beta ,\beta \)-double-Heck reaction. Tetrahedron Lett 53:7044–7051. doi:10.1016/j.tetlet.2012.10.062

  32. Fu Z, Huang S, Su W, Hong M (2010) Pd-catalyzed dearboxylative Heck coupling with dioxygen as the terminal oxidant. Org Lett 12:4992–4995. doi:10.1021/ol102158n

    Article  PubMed  CAS  Google Scholar 

  33. Konno M, Nakae T, Sakuyama S, Imaki K, Nakai H, Hamanaka N (1997) An efficient method for the synthesis of a novel leukotriene B\(_{4}\) receptor antagonist, ONO-4057, via Michael reaction of dihydroresorcinol. Synlett 12:1472–1474. doi: 10.1055/s-1997-1079

    Article  Google Scholar 

Download references

Acknowledgments

Authors are grateful to Director CSIR-IHBT for providing necessary facilities during the course of the work and financial assistance from CSIR Project ORIGIN, CSC0108. D.S. (SRF), C.B.R. (JRF), A.K.S. (SRF) gratefully acknowledge to CSIR or UGC, New Delhi, India for research fellowships.

Author information

Authors and Affiliations

  1. Natural Plant Products Division, CSIR-Institute of Himalayan Bioresource Technology, Palampur, 176061, HP, India

    Dharminder Sharma, C. B. Reddy, Arun K. Shil, Rashi Prakash Saroach & Pralay Das

Authors
  1. Dharminder Sharma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. C. B. Reddy
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Arun K. Shil
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Rashi Prakash Saroach
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Pralay Das
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Pralay Das.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (doc 4408 KB)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Sharma, D., Reddy, C.B., Shil, A.K. et al. Cyclohexyl iodide promoted approach for coumarin analog synthesis using small scaffold. Mol Divers 17, 651–659 (2013). https://doi.org/10.1007/s11030-013-9461-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11030-013-9461-y

Keywords

Search

Navigation