Synthesis and structure of a new type of C2-symmetric chiral crown ether

Tetrahedron Letters

Volumn 39, Issue 51, 1998, Pages 9493-9496

  Muraoka, Masahiro ^a   Ueda, Atsushi ^a   Zhang, Wanbin ^a   Kida, Toshiyuki ^a   Nakatsuji, Yohji ^a   Ikeda, Isao ^a   Kanehisa, Nobuko ^a   Kai, Yasushi ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

Crown ethers; Enantioselection; Molecular recognition; X ray crystal structures

Indexed keywords

18 CROWN 6 DERIVATIVE; CROWN ETHER; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; CHIRALITY; CRYSTAL STRUCTURE; ENANTIOMER; RACEMIC MIXTURE; STEREOCHEMISTRY; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 0032542131     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)02153-4     Document Type: Article

References (22)

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10. 8: C, 54.53; H, 9.15. Found: C, 54.18; H, 9.23.
11. 10: C, 55.03; H, 8.31. Found: C, 54.85; H, 8.42.
12. [7] Lipase QL (Meito Sangyo Co.), lipase PS (Amano Pharmaceutical Co.), lipase A (Amano Pharmaceutical Co.), and lipase AY (Amano Pharmaceutical Co.) were used as received without further purification.
13. 3OH mixture. The salt was a white solid.
14. 3) δ 1.05 (s, 3H, R,R-form), 1.01 (s, 3H, S,S-form), 3.52-3.75 (m, 24H).
15. [10] Both lipase PS and lipase AY disappointedly gave 75% ee and their catalytic activities were much inferior to that of lipase QL.
16. 3. The final R and Rw were 0.060 and 0.047 for 4576 observed reflections (I>1. 00σ(I)), GOF= 1.82. All measurements were made on a Rigaku AFC5R diffractometer with ß-filtered Cu-Kα radiation and a rotating anode generator. The structure was solved by direct methods [15] (SIR92), expanded using Fourier techniques [16], and refined by full-matrix least-squares techniques using the teXsan Structure analysis Software of Molecular Structure Corporation.
17. [12] Inoue, Y.; Gokel, G. W. Cation Binding by Macrocycles; Marcel Dekker, Inc.: New York, 1990.
18. [13] a) Hamilton, W. C. Acta Cryst. 1965, 18, 502.
19. b) Flack, H. D. Acta Cryst. 1983, A39, 876-881. For the anomalous dispersion analysis, models corresponding to the two enantiomeric isomers were refined separately. The (S,S) isomer gave an Rw value of 0.047, whereas the inverted (R,R) isomer could be refined under same conditions only to Rw=0. 106. This significant difference in R-values proves the absolute configuration of lariat ether 3 to be (S,S).
20. 3OD (9/1) solvent mixture [1c]. The degree of chiral recognition, △(log K), was 0.41 (log K=2.68 for the (S)-enantiomer and log K =2.27 for the (R)-form, respectively).
21. [15] SIR92: Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, M; Giacovazzo, C.; Guagliardi, A.; Polidori, G. J. Appl. Cryst. 1994, 27, 435.
22. [16] DIRDIF94: Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; de Gelder, R.; Israel, R.; Smits, J. M. M. The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands, 1994.