the Whelk-O column which indeed separates the enantiomers of
naproxen and other profens with excellent selectivity. Our results
with bisaniline 2 and citronellal demonstrate that a similar ratio-
nale, which exploits the central-to-axial chirality induction observed
upon condensation between 1 and aliphatic amines, provides a
systematic approach for the development of an ICD sensor
applicable to enantioselective analysis of a chiral aldehyde.
In summary, the remarkable ICD signals generated upon
diimine formation with the intrinsically stereodynamic sensor 2
allows unprecedented enantioselective detection of citronellal at
micromolar concentrations and quantitative ee analysis with high
accuracy. The use of 2, which is readily prepared by two
Sonogashira couplings, combines several attractive features: (1)
The generation of intense Cotton effects at high wavelength
reduces interference with chiral impurities and thus facilitates
determination of the enantiomeric composition; (2) the in situ
diimine formation and subsequent CD measurements eliminate
elaborate purification steps; (3) the CD assay is operationally
simple and requires only minute sample, sensor and solvent
amounts which reduces waste production; (4) the sensor is highly
selective for citronellal and other chiral aldehydes do not interfere
with the chiral induction and chiroptical sensing processes and
(5) this sensing method avoids the use of enantiopure derivatizing
agents which are often more expensive. Moreover, this work
shows that the concept of isostericity provides new means for the
rational design of ICD probes or stereodynamic receptors used in
chiral amplification processes.
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Funding from the National Science Foundation (CHE-1213019)
is gratefully acknowledged.
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11228 Chem. Commun., 2012, 48, 11226–11228
This journal is The Royal Society of Chemistry 2012