Skip to main content
Log in

Eco-friendly conjugate hydrocyanation of α-cyanoacrylates using potassium hexacyanoferrate(II) as cyanating reagent

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

Abstract

The conjugate hydrocyanation of α-cyanoacrylates through chemoselective 1,4-addition to synthesise α,β-dicyanopropanoates by one-pot two-step procedure using potassium hexacyanoferrate(II) as an eco-friendly cyanide source, benzoyl chloride as a promoter and potassium carbonate as a catalyst is described. The advantages of this protocol are use of a non-toxic, non-volatile and inexpensive cyanating reagent, high product yields and simple working procedure.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Aizencang, G., Frydman, R. B., Giorgieri, S., Sambrotta, L., Guerra, L., & Frydman, B. (1995). Synthesis of isoornithines and methylputrescines. An evaluation of their inhibitory effects on ornithine decarboxylase. Journal of Medicinal Chemistry, 38, 4337–4341. DOI: 10.1021/jm00021a024.

    Article  CAS  Google Scholar 

  • Das, S., Yasmin, H., Masud, M. M., Roy, S. C., Nahar, L., Rahman, M. M., Gibbons, S., Bachar, S. C., & Sarker, S. D. (2008). Total synthesis and analgesic activity of 6-fluoroindan-1-carboxylic acid. Tetrahedron, 64, 8642–8645. DOI: 10.1016/j.tet.2008.07.010.

    Article  CAS  Google Scholar 

  • Griffiths, G., Mettler, H., Mills, L. S., & Previdoli, F. (1991). Novel syntheses of gabapentin via addition of hydrocyanic acid to cyclohexylidenemalonate or cyano(cyclohexylidene) acetate. Helvetica Chimica Acta, 74, 309–314. DOI: 10.1002/hlca.19910740208.

    Article  CAS  Google Scholar 

  • Li, Z., Shi, S. Y., & Yang, J. Y. (2006). AgI-PEG400-KI catalyzed environmentally benign synthesis of aroyl cyanides using potassium hexacyanoferrate(II) as the cyanating agent. Synlett, 2006, 2495–2497. DOI: 10.1055/s-2006-950407.

    Article  Google Scholar 

  • Li, Z., Tian, G. Q., & Ma, Y. H. (2010). One-pot three-component solvent-free cyanoaroylation of aldehydes using potassium hexacyanoferrate(II) as environmentally benign cyanide source. Synlett, 2010, 2164–2168. DOI: 10.1055/s-0030-1258495.

    Article  Google Scholar 

  • Li, Z., Liu, C. H., Zhang, Y. P., Li, R. Z., Ma, B., & Yang, J. Y. (2012). Conjugate hydrocyanation of aromatic enones using potassium hexacyanoferrate(II) as an eco-friendly cyanide source. Synlett, 23, 2567–2571. DOI: 10.1055/s-0032-1317179.

    Article  CAS  Google Scholar 

  • Li, Z., Li, R.Z., Zheng, H. H., Wen, F., Li, H.B., Yin, J. J., & Yang, J. Y. (2013). Hydrocyanation of sulfonylimines using potassium hexacyanoferrate(II) as an eco-friendly cyanide source. Journal of the Brazilian Chemical Society, 24, 1739–1743. DOI: 10.5935/0103-5053.20130218.

    CAS  Google Scholar 

  • Li, Z., & Xu, J. (2014). Solvent-free synthesis of arylsulfonyl cyanides using potassium hexacyanoferrate(II) as an ecofriendly cyanide source. Phosphorus, Sulfur, and Silicon and the Related Elements, 189, 374–378. DOI: 10.1080/10426507.2013.819870.

    Article  CAS  Google Scholar 

  • Liu, Y., Shirakawa, S., & Maruoka, K. (2013). Phase-transfer-catalyzed asymmetric conjugate cyanation of alkylidene-malonates with KCN in the presence of a Brønsted acid additive. Organic Letters, 15, 1230–1233. DOI: 10.1021/ol400143m.

    Article  CAS  Google Scholar 

  • Mazet, C., & Jacobsen, E. N. (2008). Dinuclear (salen)Al complexes display expanded scope in the conjugate cyanation of α,β-unsaturated imides. Angewandte Chemie International Edition, 47, 1762–1765. DOI: 10.1002/anie.200704461.

    Article  CAS  Google Scholar 

  • Mita, T., Sasaki, K., Kanai, M., & Shibasaki, M. (2005). Catalytic enantioselective conjugate addition of cyanide to α,β-unsaturated N-acylpyrroles. Journal of the American Chemical Society, 127, 514–515. DOI: 10.1021/ja043424s.

    Article  CAS  Google Scholar 

  • Rajib, K. P., Hasina, Y., Lutfun, N., Bidyut, K. D., Abul, K. A. C., Joydeb, K. K., Siteh, C. B., & Satyajit, D. S. (2012). Synthesis of 5,6-dichloroindan-1-acids and their tetrazolyl derivatives as analgesic and anti-inflammatory agents. Medicinal Chemistry, 8, 874–882. DOI: 10.2174/157340612802084234.

    Article  Google Scholar 

  • Rappoport, Z. (1970). The chemistry of the cyano group. New York, NY, USA: Interscience Publishers. DOI: 10.1002/978047077124.

    Google Scholar 

  • Ren, Y. L., Dong, C. H., Zhao, S., Sun, Y. P., Wang, J. J., Ma, J. Y., & Hou, C. D. (2012). Copper-catalyzed cyanation of benzyl chlorides with non-toxic K4[Fe(CN)6]. Tetrahedron Letters, 53, 2825–2827. DOI: 10.1016/j.tetlet.2012.03.109.

    Article  CAS  Google Scholar 

  • Saha, D., Adak, L., Mukherjee, M., & Ranu, B. C. (2012). Hydroxyapatite-supported Cu(I)-catalysed cyanation of styrenyl bromides with K4[Fe(CN)6]: an easy access to cinna-monitriles. Organic & Biomolecular Chemistry, 10, 952–957. DOI: 10.1039/c1ob06467c.

    Article  CAS  Google Scholar 

  • Sammelson, R. E., Caboni, P., Durkin, K. A., & Casida, J. E. (2004). GABA receptor antagonists and insecticides: common structural features of 4-alkyl-1-phenylpyrazoles and 4-alkyl-1-phenyltrioxabicyclooctanes. Bioorganic & Medicinal Chemistry, 12, 3345–3355. DOI: 10.1016/j.bmc.2004.03.069.

    Article  CAS  Google Scholar 

  • Sammis, G. M., Danjo, H., & Jacobsen, E. N. (2004). Cooperative dual catalysis: Application to the highly enantioselective conjugate cyanation of unsaturated imides. Journal of the American Chemical Society, 126, 9928–9929. DOI: 10.1021/ja046653n.

    Article  CAS  Google Scholar 

  • Schareina, T., Zapf, A., & Beller, M. (2004). Improving palladium-catalyzed cyanation of aryl halides: Development of a state-of-the-art methodology using potassium hexacyanoferrate(II) as cyanating agent. Journal of Organometallic Chemistry, 689, 4576–4583. DOI: 10.1016/j.jorganchem.2004.08.020.

    Article  CAS  Google Scholar 

  • Wakita, Y., Kojima, M., Schwendner, S. W., McConnell, D., & Counsell, R. E. (1990). The synthesis and biodistribution of 3-(4′-[125I]-iodophenyl)-4-aminobutyric acid, a radioiodinated analogue of baclofen. Journal of Labelled Compounds and Radiopharmaceuticals, 28, 123–136. DOI: 10.1002/jlcr.2580280202.

    Article  CAS  Google Scholar 

  • Wang, J., Li, W., Liu, Y. L., Chu, Y. Y., Lin, L. L., Liu, X. H., & Feng, X. M. (2010). Asymmetric cyanation of activated olefins with ethyl cyanoformate catalyzed by a modular titanium catalyst. Organic Letters, 12, 1280–1283. DOI: 10.1021/ol100169r.

    Article  Google Scholar 

  • Yang, J. Y., Wang, Y. X., Wu, S. X., & Chen, F. X. (2009). The highly efficient 1,4-addition of TMSCN to aromatic enones catalyzed by CsF with water as the additive. Synlett, 2009, 3365–3367. DOI: 10.1055/s-0029-1218376.

    Article  Google Scholar 

  • Yang, J. Y., Wu, S. X., & Chen, F. X. (2010). Chiral sodium phosphate catalyzed enantioselective 1,4-addition of TM-SCN to aromatic enones. Synlett, 2010, 2725–2728. DOI: 10.1055/s-0030-1258817.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Zheng Li.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, YP., Hu, XC. & Li, Z. Eco-friendly conjugate hydrocyanation of α-cyanoacrylates using potassium hexacyanoferrate(II) as cyanating reagent. Chem. Pap. 69, 596–603 (2015). https://doi.org/10.1515/chempap-2015-0055

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1515/chempap-2015-0055

Keywords

Navigation