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Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents

Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents

Type of Publication: Journal article
URI (citable link): http://nbn-resolving.de/urn:nbn:de:bsz:352-0-264112
Author: Christl, Josefine T.; Roesle, Philipp; Stempfle, Florian; Müller, Gerhard; Caporaso, Lucia; Cavallo, Luigi; Mecking, Stefan
Year of publication: 2014
Published in: ChemSusChem ; 7 (2014), 12. - pp. 3491-3495. - ISSN 1864-5631. - eISSN 1864-564X
Pubmed ID: 25314333
DOI (citable link): https://dx.doi.org/10.1002/cssc.201402441
Summary:
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.
Subject (DDC): 540 Chemistry
Link to License: Terms of use
Bibliography of Konstanz: Yes

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CHRISTL, Josefine T., Philipp ROESLE, Florian STEMPFLE, Gerhard MÜLLER, Lucia CAPORASO, Luigi CAVALLO, Stefan MECKING, 2014. Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents. In: ChemSusChem. 7(12), pp. 3491-3495. ISSN 1864-5631. eISSN 1864-564X. Available under: doi: 10.1002/cssc.201402441

@article{Christl2014Promo-29371, title={Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents}, year={2014}, doi={10.1002/cssc.201402441}, number={12}, volume={7}, issn={1864-5631}, journal={ChemSusChem}, pages={3491--3495}, author={Christl, Josefine T. and Roesle, Philipp and Stempfle, Florian and Müller, Gerhard and Caporaso, Lucia and Cavallo, Luigi and Mecking, Stefan} }

Roesle, Philipp Roesle, Philipp Mecking, Stefan Stempfle, Florian terms-of-use Christl, Josefine T. Caporaso, Lucia 2014-12-02T09:46:29Z The 1,2-(CH<sub>2</sub>P(1-adamantyl)<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>4</sub> (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)<sub>2</sub>] (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)]<sup>+</sup> (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]<sup>+</sup> (3-PPh<sub>3</sub>). 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. Müller, Gerhard Cavallo, Luigi Stempfle, Florian Promotion of Selective Pathways in Isomerizing Functionalization of Plant Oils by Rigid Framework Substituents Christl, Josefine T. Müller, Gerhard Cavallo, Luigi 2014-12-02T09:46:29Z eng Mecking, Stefan Caporaso, Lucia 2014

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