Enhanced Methylation Rate within a Foldable Molecular Receptor
- 10 November 2004
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 69 (26) , 9234-9237
- https://doi.org/10.1021/jo048506d
Abstract
A N,N-(dimethylamino)pyridine monomer is incorporated into the backbone of a m-phenyleneethynylene oligomer such that the pyridine nitrogen is located on the interior surface of the binding cavity in the folded structure of the oligomer. For an oligomer having a chain length of 13 monomer units, competitive inhibition experiments reveal that methyl iodide binds weakly within the oligomer cavity with an association constant Ka = 2 M-1, and the oligomer−methyl iodide complex reacts with unimolecular rate constant ku = 0.082 s-1 to provide the methylated product. The effective molarity is calculated to be 230 M by comparison of ku for the 13-mer with the second-order rate constant for a 3-mer that is too short to fold and thus unable to bind methyl iodide.Keywords
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