Silicon-based thiourea-mediated and microwave-assisted thio-Michael addition under solvent-free reaction conditions
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Kamalakannan Prabakaran
,
Machindra Gund
Abstract
Silicon-based thiourea (SiliaBond® Thiourea) (Si-THU), a heterogeneous catalyst, has been applied to the highly selective C-S bond formation via Michael addition of thiols to α,β-unsaturated carbonyl compounds under solvent-free conditions at 55–60°C. The thio-Michael addition products were obtained in an excellent yield under optimised conditions. This methodology involving a metal-free as well as a metal scavenger catalyst has been found to be an alternative method for the thio-Michael addition reaction.
[1] Amini, M. M., Shaabani, A., & Bazgir, A. (2006). Tangstophosphoric acid (H3PW12O40): An efficient and eco-friendly catalyst for the one-pot synthesis of dihydropyrimidin-2(1H)-ones. Catalysis Communications, 7, 843–847. DOI: 10.1016/j.catcom.2006.02.027. http://dx.doi.org/10.1016/j.catcom.2006.02.02710.1016/j.catcom.2006.02.027Suche in Google Scholar
[2] Bandini, M., Cozzi, P. G., Giacomini, M., Melchiorre, P., Selva, S., & Umani-Ronchi, A. (2002). Sequential one-pot InBr3-catalyzed 1,4- then 1,2-nucleophilic addition to enones. Journal of Organic Chemistry, 67, 3700–3704. DOI: 10.1021/jo0163243. http://dx.doi.org/10.1021/jo016324310.1021/jo0163243Suche in Google Scholar
[3] Banerjee, S., Das, J., Alvarez, R. P., & Santra, S. (2010). Silica nanoparticles as a reusable catalyst: a straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions. New Journal of Chemistry, 34, 302–306. DOI: 10.1039/B9NJ00399A. http://dx.doi.org/10.1039/b9nj00399a10.1039/B9NJ00399ASuche in Google Scholar
[4] Barahman, M. B., & Pershang, S. (2006). Michael addition of thiols to α,β-unsaturated carbonyl compounds under solventfree conditions. ARKIVOC, 2006(12), 130–137. 10.3998/ark.5550190.0007.c15Suche in Google Scholar
[5] Chu, C. M., Gao, S., Sastry, M. N. V., & Yao, C.-F. (2005). Iodine-catalyzed Michael addition of mercaptans to α,β-unsaturated ketones under solvent-free conditions. Tetrahedron Letters, 46, 4971–4974. DOI: 10.1016/j.tetlet.2005.05.099. http://dx.doi.org/10.1016/j.tetlet.2005.05.09910.1016/j.tetlet.2005.05.099Suche in Google Scholar
[6] Falck, J. R., Lai, J.-Y., Cho, S.-D., & Yu, J. (1999). Alkylthioether synthesis via imidazole mediated Mitsunobu condensation. Tetrahedron Letters, 40, 2903–2906. DOI: 10.1016/S0040-4039(99)00390-1. http://dx.doi.org/10.1016/S0040-4039(99)00390-110.1016/S0040-4039(99)00390-1Suche in Google Scholar
[7] Firouzabadi, H., Iranpoor, N., Jafarpour, M., & Ghaderi, A. (2006). ZrOCl2 · 8H2O/silica gel as a new efficient and a highly water-tolerant catalyst system for facile condensation of indoles with carbonyl compounds under solvent-free conditions. Journal of Molecular Catalysis A: Chemical, 253, 249–251. DOI: 10.1016/j.molcata.2006.03.043. http://dx.doi.org/10.1016/j.molcata.2006.03.04310.1016/j.molcata.2006.03.043Suche in Google Scholar
[8] Jacobson, K. A. (2009). Functionalized congener approach to the design of ligands for G protein-coupled receptors (GPCRs). Bioconjugate Chemistry, 20, 1816–1835. DOI: 10.1021/bc9000596. http://dx.doi.org/10.1021/bc900059610.1021/bc9000596Suche in Google Scholar
[9] Kanagasabapathy, S., Sudalai, A., & Benicewicz, B. C. (2001). Montmorillonite K 10-catalyzed regioselective addition of thiols and thiobenzoic acids onto olefins: an efficient synthesis of dithiocarboxylic esters. Tetrahedron Letters, 42, 3791–3794. DOI: 10.1016/S0040-4039(01)00570-6. http://dx.doi.org/10.1016/S0040-4039(01)00570-610.1016/S0040-4039(01)00570-6Suche in Google Scholar
[10] Khan, F. N., Manivel, P., Prabakaran, K., Hathwar, V. R., & Akkurt, M. (2010). 5-(4-Chlorophenyl)-3-(2-furyl)-1,2,4-triazolo[3,4-a]isoquinoline. Acta Crystallographica E, 66, 1061. DOI: 10.1107/S1600536810012924. http://dx.doi.org/10.1107/S160053681001292410.1107/S1600536810012924Suche in Google Scholar PubMed PubMed Central
[11] Khan, F. N., Manivel, P., Prabakaran, K., Hathwar, V. R., & Ng, S. W. (2009a). 1-(4-Chlorophenyl)-2-phenyl-2-(3-phenyl-1-isoquinolylsulfanyl)ethanone. Acta Crystallographica E, 65, 2732. DOI: 10.1107/S1600536809041282. http://dx.doi.org/10.1107/S160053680904128210.1107/S1600536809041282Suche in Google Scholar PubMed PubMed Central
[12] Khan, F. N., Manivel, P., Prabakaran, K., Hathwar, V. R., & Ng, S. W. (2009b). 2-[2-(Cyclohexylcarbonyl)phenyl]-1-phenylethanone. Acta Crystallographica E, 65, 2745. DOI: 10.1107/S1600536809041270. http://dx.doi.org/10.1107/S160053680904127010.1107/S1600536809041270Suche in Google Scholar PubMed PubMed Central
[13] Khatik, G. L., Sharma, G., Kumar, R., & Chakraborti, A. K. (2007). Scope and limitations of HClO4-SiO2 as an extremely efficient, inexpensive, and reusable catalyst for chemoselective carbon-sulfur bond formation. Tetrahedron, 63, 1200–1210. DOI: 10.1016/j.tet.2006.11.050. http://dx.doi.org/10.1016/j.tet.2006.11.05010.1016/j.tet.2006.11.050Suche in Google Scholar
[14] Kondo, T., & Mitsudo, T. (2000). Metal-catalyzed carbon-sulfur bond formation. Chemical Reviews, 100, 3205–3220. DOI: 10.1021/cr9902749. http://dx.doi.org/10.1021/cr990274910.1021/cr9902749Suche in Google Scholar PubMed
[15] Kumar, A., & Akanksha (2007). Amino acid catalyzed thio-Michael addition reactions. Tetrahedron, 63, 11086–11092. DOI: 10.1016/j.tet.2007.08.033. http://dx.doi.org/10.1016/j.tet.2007.08.03310.1016/j.tet.2007.08.033Suche in Google Scholar
[16] Robinson, J. C., Jr., & Snyder, H. R. (1955). β-phenylethylamine. Organic Syntheses, Collective Volume 3, 720. Suche in Google Scholar
[17] Perrier, S., & Tokolpuckdee, P. (2005). Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization. Journal of Polymer Science Part A: Polymer Chemistry, 43, 5347–5393. DOI: 10.1002/pola.20986. http://dx.doi.org/10.1002/pola.2098610.1002/pola.20986Suche in Google Scholar
[18] Prabakaran, K., & Khan, F. N. (2010). Basic alumina-catalyzed, solvent-free synthesis of diversified thioethers. Phosphorus, Sulfur, and Silicon and the Related Elements, 185, 825–831. DOI: 10.1080/10426500902998131. http://dx.doi.org/10.1080/1042650090299813110.1080/10426500902998131Suche in Google Scholar
[19] Ranu, B. C., & Dey, S. S. (2004). Catalysis by ionic liquid: a simple, green and efficient procedure for the Michael addition of thiols and thiophosphate to conjugated alkenes in ionic liquid, [pmIm]Br. Tetrahedron, 60, 4183–4188. DOI: 10.1016/j.tet.2004.03.052. http://dx.doi.org/10.1016/j.tet.2004.03.05210.1016/j.tet.2004.03.052Suche in Google Scholar
[20] Salvatore, R. N., Smith, R. A., Nischwitz, A. K., & Gavin, T. (2005). A mild and highly convenient chemoselective alkylation of thiols using Cs2CO3-TBAI. Tetrahedron Letters, 46, 8931–8935. DOI: 10.1016/j.tetlet.2005.10.062. http://dx.doi.org/10.1016/j.tetlet.2005.10.06210.1016/j.tetlet.2005.10.062Suche in Google Scholar
[21] Sudalai, A., Kanagasabapathy, S., & Benicewicz, B. C. (2000). Phosphorus pentasulfide: A mild and versatile catalyst/reagent for the preparation of dithiocarboxylic esters. Organic Letters, 2, 3213–3216. DOI: 10.1021/ol006407q. http://dx.doi.org/10.1021/ol006407q10.1021/ol006407qSuche in Google Scholar PubMed
[22] Thang, S. H., Chong, (B.) Y. K., Mayadunne, R. T. A., Moad, G., & Rizzardo, E. (1999). A novel synthesis of functional dithioesters, dithiocarbamates, xanthates and trithiocarbonates. Tetrahedron Letters, 40, 2435–2438. DOI: 10.1016/S0040-4039(99)00177-X. http://dx.doi.org/10.1016/S0040-4039(99)00177-X10.1016/S0040-4039(99)00177-XSuche in Google Scholar
[23] Wight, A. P., & Davis, M. E. (2002). Design and preparation of organic-inorganic hybrid catalysts. Chemical Reviews, 102, 3589–3614. DOI: 10.1021/cr010334m. http://dx.doi.org/10.1021/cr010334m10.1021/cr010334mSuche in Google Scholar PubMed
© 2011 Institute of Chemistry, Slovak Academy of Sciences
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Artikel in diesem Heft
- 5th conference on membrane science and technology PERMEA 2010
- A procedure for the determination of dichloromethane and tetrachloroethene in water using pervaporation and gas chromatography
- Modeling of diffusive transport of benzoic acid through a liquid membrane
- Comparison of ceramic capillary membrane and ceramic tubular membrane with inserted static mixer
- New approach to regeneration of an ionic liquid containing solvent by molecular distillation
- Mass-transfer in pertraction of butyric acid by phosphonium ionic liquids and dodecane
- Determination of carbon in solidified sodium coolant using new ICP-OES methods
- Interpretation of interactions of halogenated hydrocarbons with modified silica adsorbent coated with 3-benzylketoimine group silane
- Adaptive nonlinear control of a continuous stirred tank reactor
- Anaerobic baffled reactor treatment of biodiesel-processing wastewater with high strength of methanol and glycerol: reactor performance and biogas production
- Analysis of streptolydigin degradation and conversion in cultural supernatants of Streptomyces lydicus AS 4.2501
- Spectroscopic and magnetic evidence of coordination properties of bioactive diethyl (pyridin-4-ylmethyl)phosphate ligand with chloride transition-metal ions
- Microstructure and properties of polyhydroxybutyrate-calcium phosphate cement composites
- Intercalation of basic amino acids into layered zirconium proline-N-methylphosphonate phosphate
- Effect of sol-gel preparation method on particle morphology in pure and nanocomposite PZT thin films
- Synthesis, spectroscopic and configurational study, and ab initio calculations of new diazaphospholanes
- Synthesis and in vitro antimicrobial activity of new 3-(2-morpholinoquinolin-3-yl) substituted acrylonitrile and propanenitrile derivatives
- Silicon-based thiourea-mediated and microwave-assisted thio-Michael addition under solvent-free reaction conditions
- One-pot synthesis of 2-amino-3-cyano-4-arylsubstituted tetrahydrobenzo[b]pyrans catalysed by silica gel-supported polyphosphoric acid (PPA-SiO2) as an efficient and reusable catalyst
- Comparison and optimisation of biodiesel production from Jatropha curcas oil using supercritical methyl acetate and methanol
- Determination of photoredox properties of individual kinetically labile complexes in equilibrium systems
- A halogenated coumarin from Ficus krishnae
- 4β-Isocyanopodophyllotoxins: valuable precursors for the synthesis of new podophyllotoxin analogues
- Environmentally benign one-pot synthesis and antimicrobial activity of 1-methyl-2,6-diarylpiperidin-4-ones
