Isomerisation of ω-hydroxyalkenes under hydroxycarbonylation conditions in palladium catalysed aqueous phase systems

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Abstract

The ω-hydroxyolefins 3-buten-1-ol, 3-buten-1-methyl-1-ol and 4-penten-1-ol were subjected to hydroxycarbonylation conditions in water in the presence of PdCl2(PhCN)2and 4-8 equiv. of water soluble tris(3-sodiumsulfonatophenyl)phosphine (TPPTS), or N-bis(N′,N′-diethyl-2-aminoethyl)-4-aminomethylphenyl-diphenylphosphine (N3P). Under conditions of high conversion, the olefins primarily undergo isomerisation through a chain walking mechanism with selectivities for aldehyde ranging from 65% to 98%, with the lower values for longer chain alcohols. The lactones formed as the minor product are almost exclusively branched, indicating that in the first step 2,1-insertion is strongly favoured over 1,2-insertion. In the N3P system also linear lactone is produced at lower conversion. Running the reaction in D2O produces multiple deuterium incorporation in all positions of the carbon chain. A mechanism is discussed. © 2006 Elsevier B.V. All rights reserved.

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Ionescu, A., Ruppel, M., & Wendt, O. F. (2006). Isomerisation of ω-hydroxyalkenes under hydroxycarbonylation conditions in palladium catalysed aqueous phase systems. Journal of Organometallic Chemistry, 691(18), 3806–3815. https://doi.org/10.1016/j.jorganchem.2006.05.038

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