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

Ionescu, Adriana LU ; Ruppel, Markus and Wendt, Ola LU (2006) In Journal of Organometallic Chemistry 691(18). p.3806-3815
Abstract
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... (More)
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. (Less)
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publishing date
type
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publication status
published
subject
keywords
isomerisation, hydroxycarbonylation, palladium, biphasic reactions, homogeneous catalysis
in
Journal of Organometallic Chemistry
volume
691
issue
18
pages
3806 - 3815
publisher
Elsevier
external identifiers
  • wos:000240166000013
  • scopus:33746319596
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2006.05.038
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240), Department of Chemistry (011001220)
id
89c9b7fa-422c-4c2b-9b61-6f05f9f51af6 (old id 394715)
date added to LUP
2016-04-01 16:45:47
date last changed
2022-01-28 21:55:58
@article{89c9b7fa-422c-4c2b-9b61-6f05f9f51af6,
  abstract     = {{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       = {{Ionescu, Adriana and Ruppel, Markus and Wendt, Ola}},
  issn         = {{0022-328X}},
  keywords     = {{isomerisation; hydroxycarbonylation; palladium; biphasic reactions; homogeneous catalysis}},
  language     = {{eng}},
  number       = {{18}},
  pages        = {{3806--3815}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Organometallic Chemistry}},
  title        = {{Isomerisation of omega-hydroxyalkenes under hydroxycarbonylation conditions in palladium catalysed aqueous phase systems}},
  url          = {{http://dx.doi.org/10.1016/j.jorganchem.2006.05.038}},
  doi          = {{10.1016/j.jorganchem.2006.05.038}},
  volume       = {{691}},
  year         = {{2006}},
}