Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone

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...

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Publicado: 1999
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v64_n17_p_DiNardo
http://hdl.handle.net/20.500.12110/paper_00223263_v64_n17_p_DiNardo
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00223263_v64_n17_p_DiNardo
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spelling paper:paper_00223263_v64_n17_p_DiNardo2023-06-08T14:49:31Z Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone 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. 1999 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v64_n17_p_DiNardo http://hdl.handle.net/20.500.12110/paper_00223263_v64_n17_p_DiNardo
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description 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.
title Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone
spellingShingle Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone
title_short Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone
title_full Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone
title_fullStr Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone
title_full_unstemmed Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from D-Glucoheptono-1,4-lactone
title_sort enantioselective synthesis of (2r,4s)- and (2s,4r)-4-hydroxypipecolic acid from d-glucoheptono-1,4-lactone
publishDate 1999
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v64_n17_p_DiNardo
http://hdl.handle.net/20.500.12110/paper_00223263_v64_n17_p_DiNardo
_version_ 1768545496173903872

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