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, A.P., De Lederkremer, R.M., Varela, O.
Formato: JOUR
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:http://hdl.handle.net/20.500.12110/paper_00404020_v52_n40_p12911_Nin
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_00404020_v52_n40_p12911_Nin
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spelling todo:paper_00404020_v52_n40_p12911_Nin2023-10-03T14:50:36Z 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, A.P. De Lederkremer, R.M. Varela, O. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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, A.P.
De Lederkremer, R.M.
Varela, O.
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.
format JOUR
author Nin, A.P.
De Lederkremer, R.M.
Varela, O.
author_facet Nin, A.P.
De Lederkremer, R.M.
Varela, O.
author_sort Nin, A.P.
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
url http://hdl.handle.net/20.500.12110/paper_00404020_v52_n40_p12911_Nin
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