Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids

Handle URI:
http://hdl.handle.net/10754/622684
Title:
Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids
Authors:
Goldbach, Verena; Falivene, Laura ( 0000-0003-1509-6191 ) ; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Mecking, Stefan
Abstract:
Dicarboxylic acids are compounds of high value, but to date long-chain alpha,omega-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionalization. Within this paper, we established a direct access to alpha,omega-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)(2)] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH(2))(OTf)(2) to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the Pd-II precursor, which proceeds via a reductive elimination step forming a Pd species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic system of hydroxycarbonylation ranks as one of the highest achieved for isomerizing functionalizations in combination with a high selectivity for the linear product.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Goldbach V, Falivene L, Caporaso L, Cavallo L, Mecking S (2016) Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids. ACS Catalysis 6: 8229–8238. Available: http://dx.doi.org/10.1021/acscatal.6b02622.
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
9-Nov-2016
DOI:
10.1021/acscatal.6b02622
Type:
Article
ISSN:
2155-5435; 2155-5435
Sponsors:
V.G. gratefully acknowledges support by the Carl-Zeiss-Foundation through a graduate fellowship. We thank Adrian Donner for ESI-MS measurements.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acscatal.6b02622
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGoldbach, Verenaen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorMecking, Stefanen
dc.date.accessioned2017-01-11T12:20:30Z-
dc.date.available2017-01-11T12:20:30Z-
dc.date.issued2016-11-09en
dc.identifier.citationGoldbach V, Falivene L, Caporaso L, Cavallo L, Mecking S (2016) Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids. ACS Catalysis 6: 8229–8238. Available: http://dx.doi.org/10.1021/acscatal.6b02622.en
dc.identifier.issn2155-5435en
dc.identifier.issn2155-5435en
dc.identifier.doi10.1021/acscatal.6b02622en
dc.identifier.urihttp://hdl.handle.net/10754/622684-
dc.description.abstractDicarboxylic acids are compounds of high value, but to date long-chain alpha,omega-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionalization. Within this paper, we established a direct access to alpha,omega-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)(2)] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH(2))(OTf)(2) to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the Pd-II precursor, which proceeds via a reductive elimination step forming a Pd species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic system of hydroxycarbonylation ranks as one of the highest achieved for isomerizing functionalizations in combination with a high selectivity for the linear product.en
dc.description.sponsorshipV.G. gratefully acknowledges support by the Carl-Zeiss-Foundation through a graduate fellowship. We thank Adrian Donner for ESI-MS measurements.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acscatal.6b02622en
dc.rightsThis is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.en
dc.rights.urihttp://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlen
dc.subjectisomerizing functionalizationen
dc.subjectfatty acid functionalizationen
dc.subjectwater as nucleophileen
dc.subjectPd-catalyzed carbonylationen
dc.subjectPd hydrideen
dc.subjectaqueous reaction mediumen
dc.titleSingle-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acidsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalACS Catalysisen
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionChair of Chemical Materials Science, Department of Chemistry, University of Konstanz, 78464 Konstanz, Germanyen
dc.contributor.institutionDepartment of Chemistry, University of Salerno, Via Ponte Don Melillo, 84084-Fisciano, Salerno, Italyen
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
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