Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 14, Issue 36, Pages 11512-11528Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200801377
Keywords
alcohols; asymmetric catalysis; copper; kinetic resolution; silicon
Categories
Funding
- Deutsche Forschungsgemeinschaft [Oe 249/4-1]
- Emmy Noether-Nachwuchsgruppe [Oc 249/2-3, Oe 249/2-4]
- Aventis Foundation
- Fonds der Chemischen Industrie
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Ligand-stabilized copper(I)-hydride catalyzes the dehydrogenative Si-O coupling of alcohols and silanesa process that was found to proceed without racemization at the silicon atom if asymmetrically substituted. The present investigation starts from this pivotal observation since silicon-stereogenic silanes are thereby suitable for the reagent-controlled kinetic resolution of racemic alcohols. in which asymmetry at the silicon atom enables discrimination of enantiomeric alcohols. In this full account. we summarize our efforts to systematically examine this unusual strategy of diastereoselective alcohol silylation. Ligand (sufficient reactivity with moderately electron-rich monophosphines), silane (reasonable diastereocontrol with cyclic silanes having a distinct substitution pattern) as well as substrate identification (chelating donor as a requirement) are introductorily described. With these basic data at hand, the substrate scope was defined employing enantiomerically enriched tert-butyl-substituted 1-silatetraline and highly reactive 1-silaindane. The synthetic part is complemented by the determination of the stereochemical course at the silicon atom in the Si-O coupling step followed by its quantum-chemical analysis thus providing a solid mechanistic picture of this remarkable transformation.
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