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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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author
organization
publishing date
type
Contribution to journal
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
2019-02-20 08:12:12
@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},
  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},
}