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

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 a...

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Bibliographic Details
Published in:Proceedings of the National Academy of Sciences - PNAS 2011-05, Vol.108 (22), p.8955-8959
Main Authors: Wucher, Philipp, Caporaso, Lucia, Roesle, Philipp, Ragone, Francesco, Cavallo, Luigi, Mecking, Stefan, Göttker-Schnetmann, Inigo
Format: Article
Language:English
Subjects:
Acrylates
Alkenes
Alkenes - chemistry
Atoms
Carbon - chemistry
Catalysis
Catalysts
Chemical bonds
Chemistry - methods
Chlorides
Electronics
Electrons
Ethers
Ligands
Magnetic Resonance Spectroscopy - methods
Metals - chemistry
Models, Chemical
Molecular Conformation
Molecular Structure
Molecules
Palladium
Palladium - chemistry
Pentanes
Physical Sciences
Polymerization
Polymers
Software
Stereoisomerism
Substrates
Temperature
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Summary: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.
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.1101497108