Activated carbamate reagent as chiral derivatizing agent for liquid chromatographic optical resolution of enantiomeric amino compounds

1987 ◽  
Vol 23 (12) ◽  
pp. 899-902 ◽  
Author(s):  
K. Iwaki ◽  
S. Yoshida ◽  
N. Nimura ◽  
T. Kinoshita ◽  
K. Takeda ◽  
...  
Keyword(s):  
Optical Resolution ◽  
Amino Compounds ◽  
Derivatizing Agent ◽  
Chiral Derivatizing Agent ◽  
Liquid Chromatographic

Preparation of chiral stationary phase via activated carbamate intermediate for liquid chromatographic optical resolution

1987 ◽  
Vol 23 (10) ◽  
pp. 727-730 ◽  
Author(s):  
K. Iwaki ◽  
S. Yoshida ◽  
N. Nimura ◽  
T. Kinoshita ◽  
K. Takeda ◽  
...  
Keyword(s):  
Stationary Phase ◽  
Chiral Stationary Phase ◽  
Optical Resolution ◽  
Liquid Chromatographic

Application of (S)-trifluorolactic acid for chiral derivatizing agent

1999 ◽  
Vol 97 (1-2) ◽  
pp. 213-221 ◽  
Author(s):  
Toshio Kubota ◽  
Jun Kanega ◽  
Toshimasa Katagiri
Keyword(s):  
Derivatizing Agent ◽  
Chiral Derivatizing Agent

The Theoretical Basis for Assignment by NMR

2015 ◽  
Author(s):  
Josi M. Seco ◽  
Emilio Quiqoa ◽  
Ricardo Riguera
Keyword(s):  
Absolute Configuration ◽  
Chiral Auxiliary ◽  
Primary Amines ◽  
Primary Alcohols ◽  
Chiral Reagent ◽  
Chiral Compounds ◽  
Configurational Assignment ◽  
Derivatizing Agent ◽  
Chiral Derivatizing Agent ◽  
Diastereomeric Complexes

The nuclear magnetic resonance (NMR) spectra of two enantiomers are identical. Thus, the first step in using NMR to distinguish between two enantiomers should be to produce different spectra that eventually can be associated with their different stereochemistry (i.e., the assignment of their absolute configuration). Therefore, it is necessary to introduce a chiral reagent in the NMR media. There are two ways to address this problem. One is to use a chiral solvent, or a chiral agent, that combines with each enantiomer of the substrate to produce diastereomeric complexes/associations that lead to different spectra. This is the so-called chiral solvating agent (CSA) approach; it will not be further discussed here [33–34]. The second approach is to use a chiral auxiliary reagent [13–15] (i.e., a chiral derivatizing agent; CDA) that bonds to the substrate by a covalent linkage. Thus, in the most general method, the two enantiomers of the auxiliary CDA react separately with the substrate, giving two diastereomeric derivatives whose spectral differences carry information that can be associated with their stereochemistry. The CDA method that employs arylalcoxyacetic acids as auxiliaries is the most frequently used. It can be applied to a number of monofunctionals [14–15] (secondary alcohols [35–43], primary alcohols [44–46], aldehyde [47] and ketone cyanohydrins [48–49], thiols [50–51], primary amines [52–56], and carboxylic acids [57–58]), difunctional [13] (sec/sec-1,2-diols [59–61], sec/sec-1,2-amino alcohols [62], prim/sec-1,2-diols [63–65], prim/sec-1,2-aminoalcohols, and sec/prim-1,2-aminoalcohols [66–68]), and trifunctional (prim/sec/sec-1,2,3-triols [13, 69–70]) chiral compounds. Its scope and limitations are well established, and its theoretical foundations are well known, making it a reliable tool for configurational assignment. Figure 1.1 shows a summary of the steps to be followed for the assignment of absolute configuration of a chiral compound with just one asymmetric carbon and with substituents that, for simplicity, are assumed to resonate as singlets. Step 1 (Figure 1.1a): A substrate of unknown configuration (?) is separately derivatized with the two enantiomers of a chiral auxiliary reagent, (R)-Aux and (S)-Aux, producing two diastereomeric derivatives.

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