ORGANIC
LETTERS
2005
Vol. 7, No. 14
3013-3016
Anion-Mediated Phase Transfer of
Zinc(II)-Coordinated Tyrosine Derivatives
Hua Jiang, Edward J. O’Neil, Kristy M. DiVittorio, and Bradley D. Smith*
Department of Chemistry & Biochemistry, UniVersity of Notre Dame,
Notre Dame, Indiana 46556
Received May 5, 2005
ABSTRACT
+
Tyrosine-derived Zn2 coordination complexes and their fluorescent NBD conjugates are synthesized in a short, high-yielding procedure. The
+
Zn2 complexes are highly water soluble, but in the presence of sodium laurate they readily transfer into an octanol layer. Furthermore, the
+
NBD-labeled bis-Zn2 complex can partition into vesicle membranes containing anionic phospholipids.
Synthetic Zn2+ coordination complexes have been studied
extensively as simplified models for various biological
processes,1 such as phosphate hydrolysis,2 enzyme active-
site recognition,3 receptor antagonism,4 peptidase mimicry,5
and anion sensing.6 2,2′-Dipicolylamine (DPA) is an espe-
cially versatile ligand for Zn2+, and Zn2+-DPA complexes
are known to exhibit supramolecular cooperative action. For
example, dinuclear Zn2+-DPA complexes can bind phos-
phorylated peptides in aqueous solution,6a-c while oligo-
nucleotide conjugates of Zn2+-DPA can selectively target
DNA sequences7 and hydrolyze RNA.8 Phenol derivatives
with ortho-substituted DPA units are also known to form
dinuclear Zn2+ complexes that have an affinity for phosphate
oxyanions in aqueous solution.6d-f Our interest in Zn2+-
DPA complexes stems from efforts to develop anion recep-
tors that operate in aqueous solution or on the surface of
bilayer membranes.9 Our eventual goal is to design structur-
ally complicated receptors, especially multivalent molecular
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Hamachi, I. J. Am. Chem. Soc. 2003, 125, 10184-10185. (c) Ojida, A.;
Mito-oka, Y.; Sada, K.; Hamachi, I. J. Am. Chem. Soc. 2004, 126, 2456-
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R. G.; Smith, B. D. Tetrahedron 2004, 60, 11307-11315. (c) Hanshaw, R.
G.; Hilkert, S. M.; Jiang, H.; Smith, B. D. Tetrahedron Lett. 2004, 45, 8721-
8724. (d) Hanshaw, R. G.; O’Neil, E. J.; Foley, M.; Carpenter, R. T.; Smith,
B. D. J. Mater. Chem. advance article, DOI: 10.1039/b500522a.
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Chem. ReV. 2004, 102, 699-768. (e) Aoki, S.; Kimura, E. Chem. ReV. 2004,
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10.1021/ol0510421 CCC: $30.25
© 2005 American Chemical Society
Published on Web 06/10/2005