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Abstract:

Enantiomerically pure (2R,4S)-4-hydroxypipecolic acid [(+)-1] was synthesized from D-glucoheptono-1,4-lactone (2) via the 3,5-dideoxy-D-xylo- heptono-1,4-lactone (7). The latter was readily prepared by benzoylation of 2, followed by β-elimination and diastereoselective hydrogenation of the resulting furanones (4). Compound 7 was converted into the 6,7-O- cyclohexylidene derivative 11, which on treatment with tosyl chloride for long periods afforded the 2-chloro derivative 14, the precursor of the azide 15. Hydrogenolysis of 15 and protection of the amine gave the N- benzyloxycarbonyl derivative 19, having the required configuration for the stereocenters at C-2 and C-4. Removal of the cyclohexylidene group by hydrolysis and subsequent oxidative degradation of the resulting glycol system afforded the hexurono-6,3-lactone 21 as a key intermediate. Chemoselective reduction of the aldehyde function of 21 led to the alcohol 23, which was derivatized as the mesylate 24. Releasing of the amino group by hydrogenation, and dissolution of resulting 25 in aqueous alkali, promoted the intramolecular nucleophilic displacement of the mesylate to give (+)-1. Its enantiomer [(-)-1] was prepared by a similar sequence starting from 2.

Registro:

Documento: Artículo
Título:Enantioselective synthesis of (2R,4S)- and (2S,4R)-4-hydroxypipecolic acid from D-glucoheptono-1,4-lactone
Autor:Di Nardo, C.; Varela, O.
Filiación:CIHIDECAR-CONICET, Universidad de Buenos Aires, Ciudad Universitaria, 1428, Buenos Aires, Argentina
Palabras clave:3,5 dideoxy dextro xylo heptono 1,4 lactone; 4 hydroxypipecolic acid; dextro glucoheptono 1,4 lactone; lactone derivative; pipecolic acid derivative; unclassified drug; article; drug synthesis; enantiomer; hydrogenation; hydrolysis; oxidation; stereochemistry; structure analysis
Año:1999
Volumen:64
Número:17
Página de inicio:6119
Página de fin:6125
DOI: http://dx.doi.org/10.1021/jo990445+
Título revista:Journal of Organic Chemistry
Título revista abreviado:J. Org. Chem.
ISSN:00223263
CODEN:JOCEA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v64_n17_p6119_DiNardo

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Citas:

---------- APA ----------
Di Nardo, C. & Varela, O. (1999) . Enantioselective synthesis of (2R,4S)- and (2S,4R)-4-hydroxypipecolic acid from D-glucoheptono-1,4-lactone. Journal of Organic Chemistry, 64(17), 6119-6125.
http://dx.doi.org/10.1021/jo990445+
---------- CHICAGO ----------
Di Nardo, C., Varela, O. "Enantioselective synthesis of (2R,4S)- and (2S,4R)-4-hydroxypipecolic acid from D-glucoheptono-1,4-lactone" . Journal of Organic Chemistry 64, no. 17 (1999) : 6119-6125.
http://dx.doi.org/10.1021/jo990445+
---------- MLA ----------
Di Nardo, C., Varela, O. "Enantioselective synthesis of (2R,4S)- and (2S,4R)-4-hydroxypipecolic acid from D-glucoheptono-1,4-lactone" . Journal of Organic Chemistry, vol. 64, no. 17, 1999, pp. 6119-6125.
http://dx.doi.org/10.1021/jo990445+
---------- VANCOUVER ----------
Di Nardo, C., Varela, O. Enantioselective synthesis of (2R,4S)- and (2S,4R)-4-hydroxypipecolic acid from D-glucoheptono-1,4-lactone. J. Org. Chem. 1999;64(17):6119-6125.
http://dx.doi.org/10.1021/jo990445+