Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

Josefine T. Christl; Philipp Roesle; Florian Stempfle; Gerhard J. Müller; Lucia Caporaso; Luigi Cavallo; Stefan Mecking

doi:10.1002/cssc.201402441

Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

Josefine T. Christl, Philipp Roesle, Florian Stempfle, Gerhard J. Müller, Lucia Caporaso, Luigi Cavallo, Stefan Mecking

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.

Original language	English (US)
Pages (from-to)	3491-3495
Number of pages	5
Journal	ChemSusChem
Volume	7
Issue number	12
DOIs	https://doi.org/10.1002/cssc.201402441
State	Published - Oct 14 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financing by the Stiftung Baden-Wurttemberg (Programm Umwelttechnologieforschung, U14) is acknowledged. P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. Donation of high oleic sunflower oil methyl ester by Dako AG is acknowledged.

ASJC Scopus subject areas

General Energy
Environmental Chemistry
General Materials Science
General Chemical Engineering

Access to Document

10.1002/cssc.201402441

https://repository.kaust.edu.sa/bitstream/10754/563800/1/Christl_0-264112.pdf

Cite this

@article{643c95cdff01414b84eabee01401ca41,

title = "Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents",

abstract = "The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.",

author = "Christl, {Josefine T.} and Philipp Roesle and Florian Stempfle and M{\"u}ller, {Gerhard J.} and Lucia Caporaso and Luigi Cavallo and Stefan Mecking",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financing by the Stiftung Baden-Wurttemberg (Programm Umwelttechnologieforschung, U14) is acknowledged. P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. Donation of high oleic sunflower oil methyl ester by Dako AG is acknowledged.",

year = "2014",

month = oct,

day = "14",

doi = "10.1002/cssc.201402441",

language = "English (US)",

volume = "7",

pages = "3491--3495",

journal = "ChemSusChem",

issn = "1864-5631",

publisher = "Wiley",

number = "12",

}

TY - JOUR

T1 - Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

AU - Christl, Josefine T.

AU - Roesle, Philipp

AU - Stempfle, Florian

AU - Müller, Gerhard J.

AU - Caporaso, Lucia

AU - Cavallo, Luigi

AU - Mecking, Stefan

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financing by the Stiftung Baden-Wurttemberg (Programm Umwelttechnologieforschung, U14) is acknowledged. P.R. gratefully acknowledges support from the Carl-Zeiss-Foundation by a graduate fellowship. Donation of high oleic sunflower oil methyl ester by Dako AG is acknowledged.

PY - 2014/10/14

Y1 - 2014/10/14

N2 - The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.

AB - The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.

UR - http://hdl.handle.net/10754/563800

UR - https://kops.uni-konstanz.de/bitstream/123456789/29371/1/Christl_0-264112.pdf

UR - http://www.scopus.com/inward/record.url?scp=84919386008&partnerID=8YFLogxK

U2 - 10.1002/cssc.201402441

DO - 10.1002/cssc.201402441

M3 - Article

SN - 1864-5631

VL - 7

SP - 3491

EP - 3495

JO - ChemSusChem

JF - ChemSusChem

IS - 12

ER -

Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 992440: Experimental Crystal Structure Determination : hydrido-((1,2-phenylenebis(methylene))bis(bis(adamantan-1-yl)phosphine))-triphenylphosphine-palladium(ii) trifluoromethanesulfonate methanol solvate

Cite this

Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 992440: Experimental Crystal Structure Determination : hydrido-((1,2-phenylenebis(methylene))bis(bis(adamantan-1-yl)phosphine))-triphenylphosphine-palladium(ii) trifluoromethanesulfonate methanol solvate

Cite this