Synthesis and Evaluation of Two Coumarin‐Type Derivatization Reagents for Fluorescence Detection of Chiral Amines and Chiral Carboxylic Acids

Abstract

The synthesis of two fluorescent coumarin-type chiral derivatization agents (4 and 11) is reported. A chiral side chain was introduced at position 7 of the coumarin via Mitsunobu reaction. The two coumarins bear in this side chain either a free amino group or a carboxyl group, making them useful for further transformations. Conjugates of chiral prototype drugs with 4 or 11 were prepared by amide coupling of the analyte's carboxyl group to the reagent's amine group, or vice versa. The separation of seven diastereomeric conjugates through achiral high-performance liquid chromatography (HPLC) on a common C18 column is demonstrated.

Evaluation of Pseudoenantiomeric Mixed Carbonates as Efficient Fluorogenic Probes for Enantioselectivity Screening

“…Equimolara mounts of enantiomers( R)-1 and (S)-1 were mixed to form ar acemate. [30] Ac omparison of the larger-scale E values with Quick E valuesf rom fluorometric measurements revealed good correlation. The reactions lasted from 2h to four days.…”

“…The retention times between enantiomers differed by 78 s. The use of fluorophores as derivatizing agentsi sc ommon to achieve effective separation of compounds on chromatographic columns. [30] Ac omparison of the larger-scale E values with Quick E valuesf rom fluorometric measurements revealed good correlation. Thep seudoracemic mixture simulated ar acemic mixture successfully.T his contrasts with the approximate E values (E app ) calculated from data in Table 1( showna st he ratio of relative values) which indicated high variation in the results.…”

Mixed Carbonates as Useful Substrates for a Fluorogenic Assay for Lipases and Esterases

“…Using coumarins as derivatizing agents has been reported to obtain better resolution. [30] Enantioselectivity (E) is a very helpful parameter for comparing the efficiency of various enzymes. To calculate E, the conversion and enantiomeric purity of the starting material or product must be measured.…”

Global and local interactions in the structure of crystalline 7-(diethylamino)-2-(2-oxo-2H-chromen-3-yl)chromenium perchlorate

“…Compounds containing chromenium or 2H-chromen-2-one fragments in their structure efficiently absorb radiation from the visible region and emit it in this region [2][3][4][5][6][7][8].…”

“…We synthesized this molecular ionic substance in view of the widespread occurrence of 2H-chromen-2-one (coumarin) derivatives in living matter [1] and their interesting spectral features [2,3], which can be put to use in analytics [4,5]. By combining coumarin and chromenium moieties of wellknown absorption and fluorescent abilities [3,[6][7][8] in one molecule and supplementing the latter moiety with a medium-sensitive amino group, we expected to obtain an efficient spectral probe of the acidic/basic or electrophilic/ nucleophilic properties of an environment.…”