Chiral Surfactant-Type
Catalyst: Enantioselective
Reduction of Long-Chain Aliphatic Ketoesters in Water
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Abstract
A series of amphiphilic ligands were
designed and synthesized.
The rhodium complexes with the ligands were applied to the asymmetric
transfer hydrogenation of broad range of long-chained aliphatic ketoesters
in neat water. Quantitative conversion and excellent enantioselectivity
(up to 99% ee) was observed for α-, β-, γ-, δ-
and ε-ketoesters as well as for α- and β-acyloxyketone
using chiral surfactant-type catalyst <b>2</b>. The CH/π
interaction and the strong hydrophobic interaction of long aliphatic
chains between the catalyst and the substrate in the metallomicelle
core played a key role in the catalytic transition state. Synergistic
effects between the metal-catalyzed site and the hydrophobic microenvironment
of the core in the micelle contributed to high stereoselectivity