Chiral discrimination of primary amines by HPLC after labeling with a chiral derivatization reagent, trans-2-(2,3-anthracenedicarboximido)-cyclohexanecarbonyl chloride.

Enantiomeric discrimination of chiral primary amines was performed by both reversed-phase HPLC and normal-phase HPLC after labeling with a chiral fluorescent derivatization reagent, (1R,2R)- and (1S,2S)-trans-2-(2,3-anthracenedicarboximido)cyclohexanecarbonyl chloride. Use of HPLC permits separation of diastereomeric derivatives of amines up to C30 which have a primary amino group at the middle of the alkyl chain. The derivatives of primary amines having an anteiso alkyl chain, which has a chiral branched-methyl at the n-3 position of the alkyl chain, were also separated by HPLC, and it was also possible to separate niphatesine D by reversed-phase HPLC after derivatization.

Crystalline structure of N-(S)-2-heptyl (1R,2R)-2-(2,3-anthracenedicarboximido)cyclohexanecarboxamide that differs from its preferred conformation in the solvent used for crystallization.

The crystalline structure of N-(S)-2-heptyl (1R,2R)-2-(2,3-anthracenedicarboximido)cyclohexamide (1), which was crystallized from methanol, was determined by an X-ray analysis and had a different conformation from its preferred one in CD3OD by a 1H-NMR analysis. Inter- and intra-molecular CH-pi interaction in a crystal plays a very important role in crystal packing. The preferred conformation of the amide derivative in a solution allows us to exploit (1R,2R)-2-(2,3-anthracenedicarboximido)cyclohexanecarbonyl chloride as a conversion reagent to determine the absolute configuration of chiral amines by 1H-NMR.

Chiral discrimination of secondary alcohols by both 1H-NMR and HPLC after labeling with a chiral derivatization reagent, 2-(2,3-anthracenedicarboximide)cyclohexane carboxylic acid.

Enantiomeric discrimination of chiral secondary alcohols was performed by both reversed-phase HPLC and 1H-NMR after labeling with a chiral fluorescent derivatization reagent, 2-(2,3-anthracenedicarboximide)cyclohexanecarboxylic acid. It was possible to discriminate by HPLC the chirality of alcohols up to C30 having a chiral hydroxyl group at the middle of the straight alkyl chain, and, by 1H-NMR, alcohols up to C16. For alcohols having one straight alkyl and one isoalkyl group with the same carbon numbers at both sides of a hydroxyl group, it was possible to discriminate the chiralities of alcohols up to C19 by both 1H-NMR and HPLC. The 1H-NMR methods also made it possible to determine absolute configurations empirically.

Synthesis of the four stereoisomers of 7-acetoxy-15-methylnonacosane, a component of the female sex pheromone of the screwworm fly, Cochliomyia hominivorax.

The four stereoisomers of 7-acetoxy-15-methylnonacosane (1), a component of the female sex pheromone of the New World screwworm fly (Cochliomyia hominivorax) were synthesized. The stereogenic center at C-15 of 1 originated from that of the enantiomers of citronellal, and that at C-7 was generated by lipase-catalyzed asymmetric acetylation of (3RS,11R)- and (3RS,11S)-17-methyl-1-trimethylsilylpentacos-1-yn-3-ol (13). Three of the stereoisomers of 1 showed equivalent good pheromone activity, while the activity of (7R,15R)-1 was weak.