65(P39) 不斉補助基の開発および光学分割と絶対立体化学決定への応用(ポスター発表の部)

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Camphorsultam (1) is very useful for both the enantioresolution of carboxylic acids and the determination of their absolute configurations by X-ray structure analysis. The camphorsultam amide method has the following advantages; i) a diastereomeric mixture of camphorsultam amides is easily separable by HPLC on silica gel; ii) camphorsultam amides generally crystallize as large prismatic crystals suitable for X-ray diffraction; iii) the absolute configurations of the amides obtained can be determined by the X-ray Bijvoet method using the anomalous dispersion effect of a sulfur atom and also by the internal reference method using the camphor part with known absolute configuration; iv) both the optically active carboxylic acid and camphorsultam can be easily recovered. This camphorsultam method can be extended to the cases of alcohols or amines if proper linking moieties connecting a camphorsultam group with alcohols or amines are designed, as shown in 6. We designed chiral phthalic acid amide (7) and it was found that the chiral phthalic acid amide method was effective for the enantioresolution and the determination of the absolute configurations of alcohols and amines. By this method, the obtained esters or amides were separated into enantiomers by HPLC on silica gel, and the crystalline esters or amides were subjected to X-ray structure analysis to determine their absolute configurations. In the chiral phthalic acid amide method, however, we have had difficulties like a long retention time in the chromatographic separation, because a diastereomeric mixture of some esters or amides is less soluble in the organic solvent. In order to solve this problem, the chiral dichlorophthalic acid amide method was developed. Chiral dichlorophthalic acid amide (11) enabled us to have a shorter retention time and a better separation in HPLC. These camphorsultam methods are thus very useful for the enantioresolution of carboxylic acids, alcohols and amines, and also for the determination of their absolute configurations.
天然有機化合物討論会の論文
1996-09-02

65(P39) 不斉補助基の開発および光学分割と絶対立体化学決定への応用(ポスター発表の部)

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