Enantioselective addition of diethylzinc to benzaldehyde catalyzed by a small amount of chiral 2-amino-1-alcohols

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Abstract

The reaction of diethylzinc with benzaldehyde catalyzed by a small amount of chiral 2-amino-1-alcohols in toluene at room temperature gave optically active 1-phenylpropan-1-ol almost quantitatively in ∼, 50% ee.

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    The latter products were obtained in good yields (62–68%) and high enantioselectivities (79–90% ee). Novel bipyridine-based ligands were synthesized by Jimeno and Sola to be combined with Zn(CF3CO2)2 and further investigated in enantioselective aldol reaction of cyclohexanones 142, 153 with benzaldehydes 47 [79]. Interestingly, the active catalyst was a bifunctional, cooperative self-assembled complex with a tetrahedral zinc complex forming the enamine of cyclohexanone 142, 153 through the prolinamide moiety of chiral ligand 154, whereas the thiourea group from the perpendicular achiral ligand 155 approached the aldehyde substrate through hydrogen bonding in a way that steric repulsion from the inner complex was minimized (Scheme 53).

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