Breaking the regioselectivity rule for acrylate insertion in the Mizoroki–Heck reaction

Wucher, Philipp; Caporaso, Lucia; Roesle, Philipp; Ragone, Francesco; Cavallo, Luigi; Mecking, Stefan; Göttker-Schnetmann, Inigo

Breaking the regioselectivity rule for acrylate insertion in the Mizoroki–Heck reaction

Dateien

Mecking.pdfGröße: 3.31 MBDownloads: 358

Datum

2011

Autor:innen

Wucher, Philipp

Caporaso, Lucia

Roesle, Philipp

Ragone, Francesco

Cavallo, Luigi

Mecking, Stefan

Göttker-Schnetmann, Inigo

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Proceedings of the National Academy of Sciences. 2011, 108(22), pp. 8955-8959. ISSN 0027-8424. eISSN 1091-6490. Available under: doi: 10.1073/pnas.1101497108

Zusammenfassung

In modern methods for the preparation of small molecules and polymers, the insertion of substrate carbon–carbon double bonds into metal–carbon bonds is a fundamental step of paramount importance. This issue is illustrated by Mizoroki–Heck coupling as the most prominent example in organic synthesis and also by catalytic insertion polymerization. For unsymmetric substrates H2C = CHX the regioselectivity of insertion is decisive for the nature of the product formed. Electron-deficient olefins insert selectively in a 2,1-fashion for electronic reasons. A means for controlling this regioselectivity is lacking to date. In a combined experimental and theoretical study, we now report that, by destabilizing the transition state of 2,1-insertion via steric interactions, the regioselectivity of methyl acrylate insertion into palladium–methyl and phenyl bonds can be inverted entirely to yield the opposite "regioirregular" products in stoichiometric reactions. Insights from these experiments will aid the rational design of complexes which enable a catalytic and regioirregular Mizoroki–Heck reaction of electron-deficient olefins.

Fachgebiet (DDC)

540 Chemie

Schlagwörter

Density functional theory calculation, homogeneous catalysis, organometallic, regiochemistry

Zitieren

ISO 690

WUCHER, Philipp, Lucia CAPORASO, Philipp ROESLE, Francesco RAGONE, Luigi CAVALLO, Stefan MECKING, Inigo GÖTTKER-SCHNETMANN, 2011. Breaking the regioselectivity rule for acrylate insertion in the Mizoroki–Heck reaction. In: Proceedings of the National Academy of Sciences. 2011, 108(22), pp. 8955-8959. ISSN 0027-8424. eISSN 1091-6490. Available under: doi: 10.1073/pnas.1101497108

BibTex

@article{Wucher2011-05-31Break-17554,
  year={2011},
  doi={10.1073/pnas.1101497108},
  title={Breaking the regioselectivity rule for acrylate insertion in the Mizoroki–Heck reaction},
  number={22},
  volume={108},
  issn={0027-8424},
  journal={Proceedings of the National Academy of Sciences},
  pages={8955--8959},
  author={Wucher, Philipp and Caporaso, Lucia and Roesle, Philipp and Ragone, Francesco and Cavallo, Luigi and Mecking, Stefan and Göttker-Schnetmann, Inigo}
}

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Universitätsbibliographie

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