Switching of the Diastereomer Deposited during the Crystallization of N‑[(S)‑1-Phenylethyl]-2′-carbamoyl-1,1′-binaphthalene-2-carboxylic Acid: Investigation of the Mechanism of Dielectrically Controlled Resolution

• Published in: Journal of organic chemistry Vol. 78; no. 2; pp. 597 - 605
• Main Authors: Kitamoto, Yuichi, Suzuki, Kazumi, Morohashi, Naoya, Sakai, Kenichi, Hattori, Tetsutaro
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 18.01.2013
• Subjects: Carboxylic Acids - chemistry; Crystallization; Crystallography, X-Ray; Hydrogen Bonding; Magnetic Resonance Spectroscopy; Models, Molecular; Naphthalenes - chemistry; Solvents - chemistry; Stereoisomerism
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo3024285

Dielectrically controlled resolution (DCR) has been achieved during the crystallization of (S)-1-phenylethylamides of racemic 1,1′-binaphthalene-2,2′-dicarboxylic acid (RS a,S)-1. For example, a water well-shaped plot is obtained for the diastereomeric excess (de) of the deposited amide versus the solvent permittivity (ε) for the crystallization of (RS a,S)-1 from three-component mixed solvents, consisting of 25 vol % of dichloromethane and 75 vol % of varying ratios of two solvents (i.e., an alcohol and either hexane or water). The de value drastically changes within two narrow ε ranges and diastereomerically pure crystals of either (R a,S)-1 (13.9 ≤ ε ≤ 17.9) or (S a,S)-1·CH2Cl2 (ε ≤ 11.9 and ε ≥ 21.8) deposit, depending on the solvent permittivity. X-ray crystallographic analyses reveal that the major difference between the crystal structures of (S a,S)-1 and (R a,S)-1 is the presence of solvent molecules that fill the spatial voids in the (S a,S)-1 crystals. The ε-dependence of the chemical shifts of (S a,S)-1 and (R a,S)-1 suggests that their aggregation states are similar in the same solvents and change discontinuously at two ε values. The ε-dependence of the CO stretching vibrations suggests that the lower ε is a transition point where the amide molecules, which aggregate through intermolecular hydrogen bonds in low-permittivity solvents, begin to dissociate. An absorption experiment suggests that dichloromethane is easily incorporated into solvent-free (S a,S)-1 crystals in high-permittivity solvents. On the basis of these observations, a feasible molecular mechanism is proposed for the present DCR phenomenon.