Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone

2-Acetamido-4,6-O-benzylidene-2,3-dideoxy-D-erythro-hex-2-enono-1,5-la ctone (2), readily prepared from D-glucosamine, undergoes a rearrangement on treatment with tin(IV) chloride which leads to 3-acetamido-2-pyrone (3) and 2-acetamido-2,3-dideoxy-4,6-O-formylidene-D-threo-hex-2-enono-1,5-lact one (...

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Autores principales: Nin, Alejandro Pablo, Muchnik de Lederkremer, Rosa María, Varela, Oscar José
Publicado: 1996
Materias:
4,5,6 trihydroxynorleucine
5 hydroxynorvaline
amino acid derivative
unclassified drug
article
chirality
drug synthesis
nuclear magnetic resonance
priority journal
reaction analysis
technique
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00404020_v52_n40_p12911_Nin
http://hdl.handle.net/20.500.12110/paper_00404020_v52_n40_p12911_Nin
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00404020_v52_n40_p12911_Nin
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spelling paper:paper_00404020_v52_n40_p12911_Nin2023-06-08T15:04:11Z Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone Nin, Alejandro Pablo Muchnik de Lederkremer, Rosa María Varela, Oscar José 4,5,6 trihydroxynorleucine 5 hydroxynorvaline amino acid derivative unclassified drug article chirality drug synthesis nuclear magnetic resonance priority journal reaction analysis technique 2-Acetamido-4,6-O-benzylidene-2,3-dideoxy-D-erythro-hex-2-enono-1,5-la ctone (2), readily prepared from D-glucosamine, undergoes a rearrangement on treatment with tin(IV) chloride which leads to 3-acetamido-2-pyrone (3) and 2-acetamido-2,3-dideoxy-4,6-O-formylidene-D-threo-hex-2-enono-1,5-lact one (4). A mechanism is proposed for this unusual rearrangement, which was not observed for other analogous hex-2-enono-1,5-lactones. For example, the 2-acetoxy analog of 2 (2-acetoxy-4,6-O-benzylidene-3-deoxy-D-erythro-hex-2-enono-1,5-lactone , 7) was synthesized and treated with tin(IV) chloride affording 3-acetoxy-6-chloromethyl-2-pyrone (8) as main product. The 2-pyrone derivatives 3 and 4 are convenient precursors for the synthesis of 5-hydroxynorvaline (12) and (2S,4R,5R)-4,5,6-trihydroxynorleucine (14), respectively. The latter was prepared by diastereoselective hydrogenation of 4, followed by deprotection. Fil:Nin, A.P. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:De Lederkremer, R.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1996 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00404020_v52_n40_p12911_Nin http://hdl.handle.net/20.500.12110/paper_00404020_v52_n40_p12911_Nin
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic 4,5,6 trihydroxynorleucine
5 hydroxynorvaline
amino acid derivative
unclassified drug
article
chirality
drug synthesis
nuclear magnetic resonance
priority journal
reaction analysis
technique
spellingShingle 4,5,6 trihydroxynorleucine
5 hydroxynorvaline
amino acid derivative
unclassified drug
article
chirality
drug synthesis
nuclear magnetic resonance
priority journal
reaction analysis
technique
Nin, Alejandro Pablo
Muchnik de Lederkremer, Rosa María
Varela, Oscar José
Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
topic_facet 4,5,6 trihydroxynorleucine
5 hydroxynorvaline
amino acid derivative
unclassified drug
article
chirality
drug synthesis
nuclear magnetic resonance
priority journal
reaction analysis
technique
description 2-Acetamido-4,6-O-benzylidene-2,3-dideoxy-D-erythro-hex-2-enono-1,5-la ctone (2), readily prepared from D-glucosamine, undergoes a rearrangement on treatment with tin(IV) chloride which leads to 3-acetamido-2-pyrone (3) and 2-acetamido-2,3-dideoxy-4,6-O-formylidene-D-threo-hex-2-enono-1,5-lact one (4). A mechanism is proposed for this unusual rearrangement, which was not observed for other analogous hex-2-enono-1,5-lactones. For example, the 2-acetoxy analog of 2 (2-acetoxy-4,6-O-benzylidene-3-deoxy-D-erythro-hex-2-enono-1,5-lactone , 7) was synthesized and treated with tin(IV) chloride affording 3-acetoxy-6-chloromethyl-2-pyrone (8) as main product. The 2-pyrone derivatives 3 and 4 are convenient precursors for the synthesis of 5-hydroxynorvaline (12) and (2S,4R,5R)-4,5,6-trihydroxynorleucine (14), respectively. The latter was prepared by diastereoselective hydrogenation of 4, followed by deprotection.
author Nin, Alejandro Pablo
Muchnik de Lederkremer, Rosa María
Varela, Oscar José
author_facet Nin, Alejandro Pablo
Muchnik de Lederkremer, Rosa María
Varela, Oscar José
author_sort Nin, Alejandro Pablo
title Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
title_short Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
title_full Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
title_fullStr Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
title_full_unstemmed Synthesis of (2S,4R,5R)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
title_sort synthesis of (2s,4r,5r)-4,5,6-trihydroxynorleucine and 5-hydroxynorvaline from precursors obtained by an unusual rearrangement in a 5,6-dihydro-2-pyrone
publishDate 1996
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00404020_v52_n40_p12911_Nin
http://hdl.handle.net/20.500.12110/paper_00404020_v52_n40_p12911_Nin
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