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Derivatization, complexation, and absolute configurational assignment of chiral primary amines: Application of exciton‐coupled circular dichroism
Author(s) -
Zhang Jing,
Holmes Andrea E.,
Sharma Akanksha,
Brooks Neil R.,
Rarig Randy S.,
Zubieta Jon,
Canary James W.
Publication year - 2003
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.10158
Subject(s) - chemistry , chromophore , absolute configuration , circular dichroism , steric effects , amine gas treating , derivatization , exciton , chirality (physics) , vibrational circular dichroism , cotton effect , asymmetric carbon , computational chemistry , crystallography , photochemistry , optically active , stereochemistry , organic chemistry , chiral symmetry , physics , high performance liquid chromatography , nambu–jona lasinio model , quantum mechanics , quark
We report here a sensitive method for the determination of the absolute configurations of primary amines using exciton‐coupled circular dichroism (ECCD). The method works on a microgram scale by derivatization of chiral amines with quinoline chromophores. Complexation of the chiral ligands with metal ion fixes the geometry of the chromophores, resulting in a twist that is governed by the asymmetric carbon configuration and steric environment of the amine. The absolute configurations of the primary amines can be interpreted from the couplets of the ECCD spectra of the derivatized complexes. Crystal structures, 2D NMR studies, and semiempirical calculations provide structural evidence for our model. Chirality 15:180–189, 2003. © 2003 Wiley‐Liss, Inc.