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 K3 = 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.
|Original language||English (US)|
|Number of pages||4|
|Journal||Journal of Organic Chemistry|
|State||Published - Dec 24 2004|
ASJC Scopus subject areas
- Organic Chemistry