Asymmetric Pd-catalyzed allylic substitution using a large sugar-based monophosphite ligand library. Scope and limitations.

• Authors: Sabina Alegre , Yvette Matta , Montserrat Diéguez , Oscar Pàmies
• Languages of publication: EN

Abstracts

EN

We have applied a modular sugar-based
phosphite ligand library for the Pd-catalyzed allylic
substitution reactions of several substrates. These ligands
are derived from D-(+)-glucose, D-(+)-galactose and D-(+)-
fructose, which lead to a wide range of sugar backbones,
and contain several substituents at the C-3 carbon of
the furanoside backbone and several substituents/
configurations in the biaryl moiety, with different steric
and electronic properties. Systematic variation of the
ligand parameters indicates that the catalytic performance
(activities and enantioselectivities) is highly affected by
sugar backbone, the substituents at the C-3 carbon of
the furanoside backbone, the configurations at the C-3
and C-4 carbons of the ligand backbone and the type
of substituents/configurations in the biaryl phosphite
moiety as well as the substrate type. For disubstituted
substrates moderate enantioselectivities (up to 72%) were
achieved using ligand L8d, while for monosubstituted
substrates the highest enantioselectivities (up to 40%)
were obtained using ligand L9a.

Keywords

EN

asymmetric catalysis; palladium; allylicsubstitution; phosphite ligands

• Publisher: De Gruyter Open
• Journal: Asymmetric Catalysis
• Year: 2013
• Volume: 1
• Issue: 1

Dates

online

10 - 8 - 2014

accepted

12 - 3 - 2014

received

3 - 3 - 2014

Contributors

author

Sabina Alegre

• Departament de Química Física i Inorgànica. Universitat
  Rovira i Virgili. C/ Marcelli Domingo, s/n. 43007 Tarragona,
  Spain

author

Yvette Matta

• Institute of Chemical Research of Catalonia (ICIQ), Av.
  Països Catalans 16, 43007, Tarragona, Spain

author

Montserrat Diéguez

• Departament de Química Física i Inorgànica. Universitat
  Rovira i Virgili. C/ Marcelli Domingo, s/n. 43007 Tarragona,
  Spain

author

Oscar Pàmies

• Departament de Química Física i Inorgànica. Universitat
  Rovira i Virgili. C/ Marcelli Domingo, s/n. 43007 Tarragona,
  Spain

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Identifiers

DOI

10.2478/asorg-2014-0001