Derivatives of 1-tosyl-3-amino-2-piperidone: preparation and conversion to derivatives and peptides of ornithine |
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| Authors: | V Gut J Rudinger R Walter P A Herling I L Schwartz |
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| Affiliation: | 1. Mount Sinai Medical and Graduate Schools of The City University of New York, New York, N.Y., USA;2. The Medical Research Center, Brookhaven National Laboratory, Upton, N.Y., USA;1. School of Science, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia;2. Department d’Enginyeria Quimica, Universitat Rovira I Virgili, 26 Av. dels Paisos Catalans, 43007 Tarragona, Spain;3. Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232, Australia;4. School of Science, RMIT University, Melbourne, VIC 3001, Australia;1. Key Laboratory of Pollution Processes and Environmental Criteria (Ministry of Education), China;2. College of Environmental Science and Engineering, Nankai University, Tianjin, 300350, China;1. Department of Chemical Engineering, Delft University of Technology, Van der Maasweg 9, 2629 HZ, Delft, the Netherlands;2. Wetsus–European Centre of Excellence for Sustainable Water Technology, Oostergoweg 9, 8932 PG, Leeuwarden, the Netherlands;3. University of Applied Sciences and Arts Northwestern Switzerland, Institute for Ecopreneurship, Gründenstrasse 40, 4132, Muttenz, Switzerland;4. RWTH Aachen University, Lehrstuhl für Chemische Verfahrenstechnik, Forckenbeckstr. 51, 52074, Aachen, Germany;5. Wageningen University & Research, Laboratory of Organic Chemistry, Stippeneng 4, 6708 WE, Wageningen, the Netherlands;1. Department of Chemical Engineering and Analytical Science, The University of Manchester, M13 9PL, United Kingdom;1. Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites et Nanocomposites Center, Rabat Design Center, Rue Mohamed El Jazouli, Madinat El Irfane, 10100 Rabat, Morocco;2. Laboratoire de Chimie Analytique et de Bromatologie, Faculté de Médecine et de Pharmacie, Université Mohammed V de Rabat, Rabat, Morocco;3. Mohammed VI Polytechnic University, Lot 660 Hay Moulay Rachid, Ben Guerir, 43150, Morocco |
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| Abstract: | The conversion of ditosylornithine (l-Ib) and Nα-benzyloxycarbonyl-Nδ-tosyl-ornithine (l-Ic and dl-Ic) to 1-tosylamino-2-piperidone (l-IIb) and 1-tosyl-3-benzyloxycarbonylamino-2-piperidone(l-IIc and dl-IIc) by several methods is described. The utilization of these lactams for the synthesis of ornithine peptides is illustrated. Racemic and optically active 1-tosyl-3-aminopiperidone (IIa), prepared by selective liberation of the 3-amino function of IIc, was acylated with benzyloxycarbonylglycine and benzyloxycarbonyl-l-valine to yield Va and Vb, respectively. Removal of the benzyloxycarbonyl group followed by exposure to basic conditions converted Vb to the 2,5-piperazinedione derivative (VI). Aminolysis of the optically active 2-piperidone IIc or treatment of Nα-benzyloxycarbonyl-Nδ-tosyl-l-ornithine pentachlorophenyl ester (IVb) with ammonia afforded the amide IIIb which showed no evidence of optical activity when investigated spectrophotometrically. However, removal of either the benzyloxycarbonyl group or of all the protecting groups revealed that the amide IIIb had retained full chirality. Hydrazine and glycine ethyl ester also caused ring opening of the 1-tosyl-2-piperidone derivatives IIb and IIc. The resulting amino acid and peptide derivatives IIIa, b, VIIa, b and VIIIa–c, possessing blocking groups of differentiated reactivity, are suitable intermediates for further synthesis. The mode of detosylation of ditosylornithine with hydrogen bromide in acetic acid is compared with that of the lower homologue, ditosyl-α,γ-diaminobutyric acid. |
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