ja971614f_si_001.pdf (786.04 kB)
Chiral Recognition of Dicarboxylate Anions by Sapphyrin-Based Receptors
journal contribution
posted on 1997-10-08, 00:00 authored by Jonathan L. Sessler, Andrei Andrievsky, Vladimír Král, Vincent LynchThe synthesis and characterization of the open-chain and cyclic
sapphyrin dimers 2−4 and 7,
bearing
various bisamide spacers is reported. This family of receptors was
shown to display excellent recognition properties
for various dicarboxylate anions, as judged from mass spectrometric
analyses, U-tube aqueous I/CH2Cl2/aqueous
II
through-model-membrane transport experiments, and equilibrium binding
studies. These latter were carried out in
either methanol or dichloromethane using 1H or
2H NMR and visible spectroscopic titrations. The
flexible, first-generation system 2, featuring a 1,3-bisamidopropane spacer
was found to display a high affinity for dicarboxylate
anions even in polar solvents, such as methanol. Within a range of
substrates, this receptor showed a strong preference
toward linear over bent, and aromatic over aliphatic dicarboxylate
anions, a fact that is readily rationalized in terms
of extra, stabilizing π−π, CH···π, or CH···N
interactions. This latter CH···N hydrogen-binding motif
was
observed in the single crystal structure of the 1:1 complex formed
between benzoate anion and the monoprotonated
form of sapphyrin 1a. The second-generation, open-chain
chiral sapphyrin dimers 3 and 4 (containing
(1S,2S)-1,2-bisamidocyclohexane and (S)-2,2‘-bisamido-1,1‘-binaphthalene
chiral auxiliaries, respectively) were found to form
strong complexes with N-carbobenzyloxy-protected aspartate
and glutamate anions (Ka values are on the order
of
104−105 M-1 in 19:1
(v/v) dichloromethane−methanol), and displayed a preference for
glutamate over aspartate,
with receptor 4 showing a modest level of enantiomeric
selectivity. The cyclic dimer 7 binds these anions
less
effectively, but displays excellent chiral discrimination between the
d- and l-antipodal forms of
N-carbobenzyloxy-protected glutamate anion.