Tunable Chiral Reaction Media Based on Two-Component Liquid Crystals: Regio-, Diastereo-, and Enantiocontrolled Photodimerization of Anthracenecarboxylic Acids

• Published in: Journal of the American Chemical Society Vol. 132; no. 49; pp. 17435 - 17446
• Main Authors: Ishida, Yasuhiro, Achalkumar, Ammathnadu S, Kato, Shun-ya, Kai, Yukiko, Misawa, Aya, Hayashi, Yumi, Yamada, Kuniyo, Matsuoka, Yuki, Shiro, Motoo, Saigo, Kazuhiko
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.12.2010; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; TEMPLATE POLYMERIZATION; ASYMMETRIC-SYNTHESIS; PHOTO-DIMERIZATION; STEREOCHEMISTRY; 2-ANTHRACENECARBOXYLIC ACID; GAMMA-CYCLODEXTRIN; STEREOSELECTIVE PHOTOCYCLODIMERIZATION; ORGANIC-SOLID-STATE; 2-AMINO ALCOHOLS; ARCHITECTURES
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja105221u

Three kinds of enantiopure amphiphilic amino alcohols (1a−c) were newly synthesized, of which the stereochemistry of the stereogenic carbons adjacent to the amino (C2) and hydroxy (C1) groups was systematically varied. By using these amino alcohols and four photoreactive carboxylic acids, 12 kinds of salts were prepared. The structure and thermal behavior of the salts were thoroughly investigated by various techniques, which revealed that the stereochemistry of the amino alcohol unit has significant effects on the properties of the salts; the salts of 1a with (1R,2S)-configuration did not exhibit any liquid crystal (LC) phase but showed high crystallinity, whereas 1b and 1c with (1S,2S)- and (1S)-configurations, respectively, generally afforded stable LC salts with smectic structure(s). Within the matrix of these amphiphilic salts, the in situ photodimerizations of 2-anthracenecarboxylic acid (2c) and 1-anthracenecarboxylic acid (2d) were conducted by the irradiation with UV/vis light (500 W, a high-pressure mercury arc lamp, >380 nm). Concerning reactivity and regio-/diastereo-/enantioselectivities, the LC phases were found to be superior to isotropic and crystalline phases. For the two substrates 2c and 2d, every LC phase promoted the photodimerization with unprecedentedly high head-to-head selectivity. Particularly in the case of 2c, diastereoselecitivity (syn HH vs anti HH) could be rationally controlled by the choice of the amino alcohol unit and mesophase (syn HH:anti HH = 61:37 to 26:72). Moreover, one of the LC phases exhibited by 1b·2c afforded the anti HH-dimer of 2c with excellent enantioselectivity (up to 86% ee). On the basis of the hypothesis that the present photochemical outcome arises from the preorientation of the substrates, a preliminary structural model of these LCs was proposed.