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Phosphorus‐Bearing Axially Chiral Biaryls by Catalytic Asymmetric Cross‐Cyclotrimerization and a First Application in Asymmetric Hydrosilylation
Author(s) -
Heller Barbara,
Gutnov Andrey,
Fischer Christine,
Drexler HansJoachim,
Spannenberg Anke,
Redkin Dmitry,
Sundermann Corinna,
Sundermann Bernd
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600826
Subject(s) - hydrosilylation , moiety , denticity , chemistry , catalysis , axial symmetry , enantioselective synthesis , phosphine , axial chirality , ligand (biochemistry) , stereochemistry , combinatorial chemistry , organic chemistry , crystal structure , physics , receptor , biochemistry , quantum mechanics
A novel and efficient, two‐step route to axially chiral biaryls is demonstrated. In a direct asymmetric cross‐cyclotrimerization in the presence of a chiral cobalt(I) catalyst, axially chiral biaryls bearing phosphoryl moieties have been prepared, and through indirect evidence the authors have been able to clarify the origin of the stereochemical induction and the nature of the central intermediate in the catalytic cycle. By subsequent reduction of the phosphoryl moiety to the corresponding phosphine, a very efficient and atom‐economical approach to chiral systems has been developed. These chiral systems clearly have great potential use as axially chiral monodentate P‐ or bidentate P,O‐ligands, as has been demonstrated by the employment of the novel NAPHEP as a new monodentate acting ligand in an asymmetric hydrosilylation reaction.