Catalyzing methanolysis of alkyl halides in the interior of an amphiphilic molecular basket

Organic Letters

Volumn 9, Issue 25, 2007, Pages 5147-5150

  Ryu, Eui Hyun ^a   Cho, HongKwan ^a   Zhao, Yan ^a  

^a IOWA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 37249060326     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol701883u     Document Type: Article

References (22)

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17. Phase separation of solvents can be also realized by reversed micelles formed by the aggregation of conventional surfactants - e.g., a pool of water is typically used to stabilize reversed micelles formed by surfactants. Even though reversed micelles have been studied extensively as reaction media for reactions, their interior tend to be much larger (depending on the amount of water added) than small organic molecules. For catalysis in micelles and reversed micelles, see: Fendler, J. H.; Fendler, E. J. Catalysis in Micelles and Macromolecular Systems; Academic Press: London, 1975.
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20. It is difficult to design experiments to determine whether the size or the hydrophobicity of the substrate is more important under these conditions. Attaching hydrophobic groups to the substrate, as in this study, increases both its size and hydrophobicity. Attaching hydrophilic groups (to increase the size and decrease the hydrophobicity) is problematic. Hydrophilic groups typically have heteroatoms that may interfere with the solvolysis, e.g., through neighboring group participation. Also, the hydrophilic groups themselves are likely to alter the local solvent composition around the substrate and change the rate of methanolysis.
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22. Recently, we reported a porphyrin catalyst with cholate groups around the catalytic center, see: Zhou, Y.; Ryu, E.-H.; Zhao, Y.; Woo, L. K. Organometallics 2007, 26, 358-364.