Convenient, enantioselective hydrosilylation of imines in protic media catalyzed by a Zn-trianglamine complex

• Published in: Organic & biomolecular chemistry Vol. 9; no. 10; pp. 3863 - 3870
• Main Authors: Gajewy, Jadwiga, Gawronski, Jacek, Kwit, Marcin
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 21.05.2011
• Subjects: Catalysis; Chemistry; Chemistry, Organic; Imines - chemistry; Macrocyclic Compounds - chemistry; Models, Molecular; Molecular Conformation; Organometallic Compounds - chemistry; Physical Sciences; Quantum Theory; Science & Technology; Silicon - chemistry; Solvents - chemistry; Stereoisomerism; Substrate Specificity; Zinc - chemistry; ASYMMETRIC HYDROSILYLATION; KETONES; REDUCTION; POLYMETHYLHYDROSILOXANE
• ISSN: 1477-0520; 1477-0539; 1477-0539
• DOI: 10.1039/c1ob05074e

Chiral hexamine macrocycle derived from trans-1,2-diaminocyclohexane (DACH) in a complex with diethylzinc efficiently catalyzes the asymmetric hydrosilylation of N-phosphorylated aryl-alkyl or aryl-aryl ketimines in protic media with enantiomeric excess of the product approaching 100%. The cyclic structure of the trianglamine ligand increases the enantioselectivity and/or the yield of the reaction, in comparison to the catalysis by acyclic N,N'-dibenzyl-DACH ligands. Density functional theory (DFT) computations on the structure of the model ligand-zinc complex and on the structures of the pre-organized reactants together with the calculations of possible transition states allow rationalization of the direction of the asymmetric induction of the hydrosilylation reaction. This is the first example of asymmetric catalysis of the hydrosilylation reaction of ketimines with the use of a readily available and inexpensive macrocyclic trianglamine ligand.