Chiral derivitizing agent
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A chiral derivitizing agent (CDA) also known as a chiral resolving reagent, is a chiral auxiliary which can convert a mixture of enantiomers into diastereomers in order to analyse the quantities of each enantiomer present within the mix. In NMR spectroscopy these compounds are called chiral shift reagents.
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[edit] History
Since NMR spectroscopy has been available to chemists, there have been numerous studies on the applications of this technique. One of these noted the difference in the chemical shift (i.e. the distance between the peaks) of two diastereomers.[1] It was reasoned that if a mix of enantiomers could be converted into a mix of diastereomers then it would be possible to distinguish them using NMR. As a result Harry S. Mosher, et al came up with MTPA (α-methoxy-α-(trifluoromethyl)phenylacetic acid), also known as Mosher's acid.[2]. The corresponding acid chloride is also known as Mosher's acid chloride, and the resultant diastereomeric esters are known as Mosher's esters.
Since then, other methods have been developed. At first, they were based on MPTA. Later, the principles were extended to phosphorus and boron systems. Research is still continuing on in this area and the limitations of CDA's as a valid test for enantiopurity are becoming fewer as more systems are designed.
[edit] Mosher's acid
Mosher's acid or acid chloride reacts easily with alcohols and amines to give esters and amides respectively. This method is able to determine the configuration of simple chiral amines and alcohols[3] The reason racemization does not occur is because there is no α-Hydrogen near the carboxyl group (therefore it cannot form an enol). This allows it to react with alcohol or amine to form an MPTA ester or amide respectively.
[edit] References
- ^ Cram D. J.; Am. Chem. Soc. 1959, 81, 2756
- ^ Mosher H. S.; Dale J. A.; Dull D. L.; J. Org. Chem. 1969 34, 2543
- ^ Parker D.; NMR Determination of Enantiopurity; Chem. Rev. 1991, 91, 1441
[edit] See also
Principles: Chirality, Stereoisomer, Enantiomer, Diastereomer
Analysis: Optical rotation, Enantiomeric excess, Diastereomeric excess, Chiral derivitizing agents
Chiral resolution: Crystallization, Kinetic resolution, Chiral column chromatography
Reactions: Asymmetric induction, Chiral reagents, Chiral pool synthesis, Chiral auxiliaries, Asymmetric catalytic reduction, Asymmetric catalytic oxidation, Organocatalysis, Biocatalysis
