Degradingdehydroabietylisothiocyanate as a chiral derivatizing reagent for enantiomeric separations by capillary electrophoresis

Abstract

Abietic acid is a naturally occurring enantiomeric diterpenic acid. Its absolute optical purity and very stable stereochemistry structure makes it an excellent starting material for preparing chiral derivatizing reagents for chromatographic or electrophoretic applications. This paper describes the synthesis and evaluation of a novel chiral derivatization reagent, i.e., degradingdehydroabietylisothiocyanate (DDHAIC) derived from dehydroabietic acid. Its applicability for the enantioseparation of racemic amino acids by CE was demonstrated. DDHAIC reacted readily with amino acids at an elevated temperature (70 degrees C). The resulting derivatives were highly stable and separable by MEKC. Separation of amino acid-DDHAIC diastereomers was achieved with a running buffer consisting of 50 mM Na(2)HPO(4) (pH 9.0), 18 mM SDS, and 25% v/v ACN. Under the conditions selected, diastereomers formed from ten pairs of tested amino acid enantiomers including D/L-Asn, D/L-Met, D/L-Leu, D/L-Phe, D/L-Trp, D/L-Ser, D/L-Val, D/L-Ala, D/L-Thr, and R/S-vigabatrin were well resolved. The resolution values were in the range of 0.95-8.9.

Recent progress in capillary electrophoretic analysis of amino acid enantiomers

“…To form diastereoisomer, several chiral reagents such as (+)-or (−)-1-(9-anthryl)-2-propyl chloroformate (APOC) [183,184], FMOC-l-alanyl Ncarboxyanhydride (FMOC-l-Ala-NCA) [185], dehydroabietylisothiocyanate (DHAIC) [186,187], degrading dehydroabietylisothiocyanate (DDHAIC) [188] and R(−)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl)-2,1,3-benzoxadiazole (DBDPyNCS) [189] have been employed in CE.…”

Recent developments of enantioseparation techniques for adrenergic drugs using liquid chromatography and capillary electrophoresis: A review

“…Indirect separations are based on diastereomer formation through precolumn derivatization using a chiral derivatizing reagent followed by separating the diastereomers with an achiral running buffer [156]. Several chiral derivatization reagents used in HPLC have also been applied in CE.…”

Recent advances in amino acid analysis by CE

“…Dehydroabietylisothiocyanate (DHAIC), which is derived from dehydroabietic acid, was synthesized as a chiral derivatization reagent [57]. When this reagent reacts with AAs at 707C in ACN, stable derivatives can be detected using UVabsorption detection.…”