A hydrophosphination reaction that is free of base, acid and catalyst, using only 2-methyltetrahydrofuran as additive has been performed. A new family of mono-, di-, tri- and tetra-phosphines compounds are obtained in good to excellent yields by adding diphenylphosphine to alkenes, mono- and polyfunctional acrylics (based on acrylate and methacrylate motifs) and acrylamide substrates. Addition of four equivalent of bio-mass derived 2-MeTHF into the reaction media improves both conversion and time of the reaction and reduces the sensitivity of the reactants over oxidation. This simple, straightforward and atom-economic method respects the principles of Green Chemistry. Furthermore, in each case this transformation shows an exclusive regioselectivity towards the anti-Markovnikov products.
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http://dx.doi.org/10.1039/c9ra04896k | DOI Listing |
J Org Chem
November 2020
Institut für Anorganische und Analytische Chemie der Universität Münster, Corrensstraße 30, D-48149 Münster, Germany.
3H-Phosphaallenes are accessible on a new and facile route and show a fascinating chemical behavior. The thermally induced rearrangement of Mes*P═C═C(H)R' (R' = Bu, Ad) afforded by C-H activation, isobutene elimination, and C-C and P-H bond formation bicyclic 1-benzo-dihydrophosphetes () with PC heterocycles. DFT calculations suggest a mechanism with intramolecular nucleophilic aromatic substitution and replacement of an alkyl group by the nucleophilic α-C atom of the phosphaallene.
View Article and Find Full Text PDFRSC Adv
August 2019
Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg, CNRS UMR 7504 23 Rue du Loess, BP 43 F-67034 Strasbourg Cedex 2 France
A hydrophosphination reaction that is free of base, acid and catalyst, using only 2-methyltetrahydrofuran as additive has been performed. A new family of mono-, di-, tri- and tetra-phosphines compounds are obtained in good to excellent yields by adding diphenylphosphine to alkenes, mono- and polyfunctional acrylics (based on acrylate and methacrylate motifs) and acrylamide substrates. Addition of four equivalent of bio-mass derived 2-MeTHF into the reaction media improves both conversion and time of the reaction and reduces the sensitivity of the reactants over oxidation.
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