Structure and mechanism in Cinchona alkaloid chemistry: Aqueous hydrolysis proceeds with complete inversion or complete retention of configuration

Angewandte Chemie - International Edition

Volumn 39, Issue 12, 2000, Pages 2085-2087

  Braje, Wilfried M ^a   Holzgrefe, Jens ^a   Wartchow, Rudolf ^a   Hoffmann, H Martin R ^a  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

Author keywords

Alkaloids; Hydrolyses; Molecular recognition; Nitrogen heterocycles

Indexed keywords

CINCHONA ALKALOID; MESYLIC ACID; QUINIDINE; QUININE;

ARTICLE; CONFORMATIONAL TRANSITION; CRYSTAL STRUCTURE; DRUG CONFORMATION; DRUG HYDROLYSIS; DRUG TRANSFORMATION; HYDROGEN BOND; MOLECULAR RECOGNITION; REACTION ANALYSIS; SOLVATION; STEREOCHEMISTRY; X RAY DIFFRACTION;

EID: 0034674280     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000616)39:12<2085::AID-ANIE2085>3.0.CO;2-N     Document Type: Article

References (32)

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6. Naturally occurring carboxylic acids other than tartaric acid were also investigated, but gave some minor side products. The order of decreasing selectivity was: tartaric acid > malic acid, succinic acid, citric acid > mandelic acid > lactic acid, p-toluenesulfonic acid, sulfuric acid.
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15. [7] is strongly solvent dependent. This ring expansion involves fission of two σ-bonds and takes place, for example, with silver benzoate in methanol or with silver benzoate in anhydrous acetone.
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19. 3) as syn, open (Figure 1 b).
20. Generation of a stabilized intermediate carbocation seems facile, because the π electron cloud of the quinoline moiety is oriented correctly for overlap with the vacant p orbital at C9 (Figure 1 b). Hydration of the (protonated) bridgehead nitrogen and of the leaving group in the syn, open conformation is thought to favor nucleophilic attack of the carbocation from the front. Nonetheless, since the intermediate cation is delocalized and comparatively long-lived, the stereochemical outcome, that is complete retention of configuration, is remarkable.
21. 1-Phenylethyl halides (PhCH(Me)-X; X = Cl, Br), which may be considered as models for our O-mesyl cinchonanes and 2, have been reported to solvolyse in aqueous ethanol with substantial racemization and up to 27% inversion of configuration. See: C. K. Ingold, Structure and Mechanism in Organic Chemistry, 2nd ed., Cornell University Press, Ithaca, 1969, p. 521, Table 33-1.
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29. Further recent works in the field of Cinchona alkaloids: a) W. M. Braje, J. Frackenpohl, O. Schrake, R. Wartchow, W. Beil, H. M. R. Hoffmann, Helv. Chim. Acta 2000, 83, 777;
30. b) S. Röper, J. Frackenpohl, O. Schrake, R. Wartchow, H. M. R. Hoffmann, Org. Lett. 2000, 2, in press;
31. c) J. Frackenpohl, H. M. R. Hoffmann, J. Org. Chem. 2000, 65, in press.
32. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-115799 (5) and -115802 (2). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44) 1223-336-013; e-mail: deposit@ccdc.cam. ac.uk.