A Homochiral Porous Metal−Organic Framework for Highly Enantioselective Heterogeneous Asymmetric Catalysis

• Published in: Journal of the American Chemical Society Vol. 127; no. 25; pp. 8940 - 8941
• Main Authors: Wu, Chuan-De, Hu, Aiguo, Zhang, Lin, Lin, Wenbin
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 29.06.2005; Amer Chemical Soc
• Subjects: Aldehydes - chemical synthesis; Aldehydes - chemistry; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Multidisciplinary; Crystallography, X-Ray; Exact sciences and technology; General and physical chemistry; Hydrogen Bonding; Ion-exchange; Ligands; Models, Molecular; Molecular Structure; Organometallic Compounds - chemistry; Physical Sciences; Porosity; Science & Technology; Stereoisomerism; Surface physical chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Titanium - chemistry; Zeolites: preparations and properties; COORDINATION; SQUARE; MOLECULES; Zinc Organic compounds; Catalytic reaction; Enantioselectivity; Catalyst selectivity; Organic ligand; Transition metal Complexes; Complex catalyst; Experimental study; Lattice parameters; Molecular sieve; Chemical coupling; Cadmium Complexes; Asymmetric reaction; Chloro complex; Catalyst activity
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja052431t

A homochiral porous noninterpenetrating metal−organic framework (MOF), 1, was constructed by linking infinite 1D [Cd(μ-Cl)2] n zigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The secondary chiral dihydroxy groups accessible via the large open channels in 1 were utilized to generate a heterogeneous asymmetric catalyst for the addition of diethyzinc to aromatic aldehydes to afford chiral secondary alcohols at up to 93% enantiomeric excess (ee). Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.