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

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

60 Scopus citations

Abstract

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 H 2C = 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.

Original languageEnglish (US)
Pages (from-to)8955-8959
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume108
Issue number22
DOIs
StatePublished - May 31 2011

Keywords

  • Density functional theory calculation
  • Homogeneous catalysis
  • Organometallic
  • Regiochemistry

ASJC Scopus subject areas

  • General

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