Copper(II)-Catalyzed Hydrosilylation of Ketones Using Chiral Dipyridylphosphane Ligands: Highly Enantioselective Synthesis of Valuable Alcohols
| Autor: | Feifei Wu, Feng Yu, Yao-Zong Sui, Albert S. C. Chan, Lin-Jie Xie, Ji‐Ning Zhou, Xi-Chang Zhang, Jing Wu |
|---|---|
| Rok vydání: | 2011 |
| Předmět: |
Molecular Structure
Chemistry Hydrosilylation Aryl Organic Chemistry Enantioselective synthesis Stereoisomerism Alcohol General Chemistry Ketones Ligands Amino Alcohols Catalysis chemistry.chemical_compound Alcohols Styrene oxide Epoxy Compounds Organic chemistry Organosilicon Compounds Stereoselectivity Enantiomer Enantiomeric excess Oxidation-Reduction Copper |
| Zdroj: | Chemistry - A European Journal. 17:14234-14240 |
| ISSN: | 0947-6539 |
| Popis: | In the presence of PhSiH(3) as the reductant, the combination of enantiomeric dipyridylphosphane ligands and Cu(OAc)(2)·H(2)O, which is an easy-to-handle and inexpensive copper salt, led to a remarkably practical and versatile chiral catalyst system. The stereoselective formation of a selection of synthetically interesting β-, γ- or δ-halo alcohols bearing high degrees of enantiopurity (up to 99.9% enantiomeric excess (ee)) was realized with a substrate-to-ligand molar ratio (S/L) of up to 10,000. The present protocol also allowed the hydrosilylation of a diverse spectrum of alkyl aryl ketones with excellent enantioselectivities (up to 98% ee) and exceedingly high turn-over rates (up to 50,000 S/L molar ratio in 50 min reaction time) in air, under very mild conditions, which offers great opportunities for the preparation of various physiologically active targets. The synthetic utility of the chiral products obtained was highlighted by the efficient conversion of optically enriched β-halo alcohols into the corresponding styrene oxide, β-amino alcohol, and β-azido alcohol, respectively. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text