Isomerisation of omega-hydroxyalkenes under hydroxycarbonylation conditions in palladium catalysed aqueous phase systems
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/394715
- author
- Ionescu, Adriana LU ; Ruppel, Markus and Wendt, Ola LU
- organization
- publishing date
- 2006
- 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
- 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}}, }