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Article title

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

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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.
Physical description
10 - 8 - 2014
12 - 3 - 2014
3 - 3 - 2014
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