ORGANIC
LETTERS
2
009
Vol. 11, No. 16
654-3657
The Influence of Amine Functionalities
on Anion Binding in
Polyamide-Containing Macrocycles
3
Sung Ok Kang, Victor W. Day, and Kristin Bowman-James*
Department of Chemistry, UniVersity of Kansas, Lawrence, Kansas 66045
Received June 23, 2009
ABSTRACT
Mixed amide/amine macrocyclic anion hosts of varying sizes and with different amine substituents have been synthesized and characterized.
4-
Host 2, containing a 28-membered ring and secondary amines, has shown selective binding for HSO over other oxo anions and halides in
72-
DMSO-d
6
using NMR titrations. Crystal structures of SO
4
2-, HPO
macrocyclic conformations depending on the N-substituent. Anion affinities appear to be correlated with macrocycle conformation.
4
2-, H
2
PO
4
-, and H
2 2
P O
with the 28-membered ring hosts indicate different
Widespread interest in understanding the underlying concepts
of anion coordination chemistry has led to the design and
and enzymes. For example, the phosphate and sulfate binding
proteins (PBP and SBP, respectively) are biological anion
hosts that show selective binding for tetrahedral anions.
1,2
3,4
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synthesis of a variety of anion receptors. Polyamine and
5
-11
polyamide
macrocycles have been agressively pursued
in this regard. Polyamines display generally high affinities
for anions, especially in their polyprotonated forms. Polya-
mides play a major role as biological receptors in proteins
(
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10.1021/ol9014249 CCC: $40.75
Published on Web 07/29/2009
2009 American Chemical Society