Rice straw ash extract, an efficient solvent for regioselective hydrothiolation of alkynes
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Herein, we describe a simple and inexpensive protocol for the hydrothiolation of alkynes. In this context, water extract of rice straw ash (WERSA) has been proven to be a green, mild and efficient solvent for the preparation of vinyl thioethers. Generally, it was found that alkyne and thiol derivatives were excellent reaction partners, producing the corresponding products with good yields and good stereoselectivity with the predominant formation of the Z isomer. Moreover, WERSA was recovered and reused for further catalytic reactions without a significant loss of activity.
KeywordsWERSA Hydrothiolation Alkynes Alkenes Thiols Agro-waste
We gratefully acknowledge the National Council for Scientific and Technological Development—CNPq, CAPES and FAPERGS-Pronex for financial support. The authors are also grateful to CIA-FURG for the NMR analysis and the Program of Support for the Publication of Academic Production/PROPESP/FURG/2018. CAPES and PET-FURGSAP are also acknowledged for the fellowship for A. L. and L. M. C. B., respectively. Funding was provided by Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (Grant No FAPERGS/CNPq 12/2014 - PRONEX) and National Council for Scientific and Technological Development-CNPq (Grant No 428494/2018-8).
- Banerjee S, Das J, Alvarez RP, 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 J Chem 34:302–306. https://doi.org/10.1039/b9nj00399a CrossRefGoogle Scholar
- Corma A, González-Arellano C, Iglesias M, Sánchez F (2010) Efficient synthesis of vinyl and alkyl sulfides via hydrothiolation of alkynes and electron-deficient olefins using soluble and heterogenized gold complexes catalysts. Appl Catal A Gen 375:49–54. https://doi.org/10.1016/j.apcata.2009.12.016 CrossRefGoogle Scholar
- Kundu D, Chatterjee T, Ranu BC (2013) Magnetically separable CuFe2O4 nanoparticles catalyzed ligand-free C–S coupling in water: access to (E)- and (Z)-styrenyl-, heteroaryl and sterically hindered aryl sulfides. Adv Synth Cat 355:2285–2296. https://doi.org/10.1002/adsc.201300261 CrossRefGoogle Scholar
- Malyshev DA, Scott NM, Marion N, Stevens ED, Ananikov VP, Beletskaya IP, Nolan SP (2006) Homogeneous nickel catalysts for the selective transfer of a single arylthio group in the catalytic hydrothiolation of alkynes. Organometallics 25:4462–4470. https://doi.org/10.1021/om060302v CrossRefGoogle Scholar
- Modem S, Kankala S, Balaboina R, Thirukovela NS, Jonnalagadda SB, Vadde R, Vasam CS (2016) Decarbonylation of salicylaldehyde activated by p-cymene ruthenium(II) dimer: implication for catalytic alkyne hydrothiolation. Eur J Org Chem 2016:4635–4642. https://doi.org/10.1002/ejoc.201600809 CrossRefGoogle Scholar
- Palacios L, Giuseppe AD, Artigas MJ, Polo V, Lahoz FJ, Castarlenas R, Pérez-Torrente J, Oro LA (2016) Mechanistic insight into the pyridine enhanced α-selectivity in alkyne hydrothiolation catalysed by quinolinolate–rhodium(ǀ)–N-heterocyclic carbine complexes. Catal Sci Technol 6:8548–8561. https://doi.org/10.1039/c6cy01884j CrossRefGoogle Scholar
- Rosa CH, Peixoto MLB, Rosa GR, Godoi B, Galetto FZ, D’Oca MGM, Godoi M (2017) Sulfamic acid: an efficient and recyclable catalyst for the regioselective hydrothiolation of terminal alkenes and alkynes with thiols. Tetrahedron Lett 58:3777–3781. https://doi.org/10.1016/j.tetlet.2017.08.051 CrossRefGoogle Scholar