Highly Selective Supramolecular Catalyzed Allylic Alcohol Isomerization

A supramolecular tetrahedral assembly Na12[Ga4L6] (L = 1,5-bis-catecholamide naphthalene) has been found to selectively encapsulate monocationic rhodium complexes of the appropriate size and shape. Encapsulation within the chiral environment of the host directly affects the symmetry of the rhodium g...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2007-03, Vol.129 (10), p.2746-2747
Main Authors: Leung, Dennis H, Bergman, Robert G, Raymond, Kenneth N
Format: Article
Language:English
Subjects:
Catalysis
Enzymes - chemistry
Isomerism
Magnetic Resonance Spectroscopy
Molecular Mimicry
Molecular Structure
Propanols - chemistry
Rhodium
Substrate Specificity
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Summary:A supramolecular tetrahedral assembly Na12[Ga4L6] (L = 1,5-bis-catecholamide naphthalene) has been found to selectively encapsulate monocationic rhodium complexes of the appropriate size and shape. Encapsulation within the chiral environment of the host directly affects the symmetry of the rhodium guest and can be well characterized by NMR spectroscopy. The rhodium complexes were found to be catalytically active for the isomerization of allylic alcohols. Investigations into the catalytic activity of the encapsulated rhodium guests have shown that the constrained cavity of the host exerts a strong influence on the reactivity at the metal center. The supramolecular host prevents substrates of the wrong size and shape from entering the host cavity and reacting with the encapsulated metal center, while substrates of the correct dimensions are allowed ready access. These results suggest that the metal center remains in the active site of the host while reactants and products freely and rapidly access the host cavity.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja068688o