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

Summary, in English

The omega-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)(2) and 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. (c) 2006 Elsevier B.V. All rights reserved.

• Author: Adriana Ionescu; Markus Ruppel; Ola Wendt
• Department/s: Department of Chemistry; Centre for Analysis and Synthesis
• Publishing year: 2006
• Language: English
• Pages: 3806-3815
• Publication/Series: Journal of Organometallic Chemistry
• Volume: 691
• Issue: 18
• Links: http://dx.doi.org/10.1016/j.jorganchem.2006.05.038
• Document type: Journal article
• Publisher: Elsevier
• Topic: Organic Chemistry
• Keywords: isomerisation; hydroxycarbonylation; palladium; biphasic reactions; homogeneous catalysis
• Status: Published
• ISBN/ISSN/Other: ISSN: 0022-328X