- A simple chromatographic route for the isolation of meso diaminopimelic acid
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Meso diaminopimelic acid is an important noncoded amino acid found in Gram-negative bacterial peptidoglycan. In spite of its importance, this stereoisomer is not available commercially. A simple, economical procedure was developed for the isolation of pur
- Toth, Gabor K.,Hetenyi, Anasztazia,Ilisz, Istvan,Peter, Antal
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experimental part
p. 133 - 137
(2011/11/05)
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- Enantiomerically pure α-amino acid synthesis via hydroboration - Suzuki cross-coupling
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The Garner aldehyde-derived methylene alkene 5 and the corresponding benzyloxycarbonyl compound 25 undergo hydroboration with 9-BBN-H followed by palladium-catalyzed Suzuki coupling reactions with aryl and vinyl halides. After one-pot hydrolysis -oxidation, a range of known and novel nonproteinogenic amino acids were isolated as their N-protected derivatives. These novel organoborane homoalanine anion equivalents are generated and transformed under mild conditions and with wide functional group tolerance: electron-rich and -poor aromatic iodides and bromides (and a vinyl bromide) all undergo efficient Suzuki coupling. The extension of this methodology to prepare meso-DAP, R,R-DAP, and R,R-DAS is also described.
- Collier, Philip N.,Campbell, Andrew D.,Patel, Ian,Raynham, Tony M.,Taylor, Richard J. K.
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p. 1802 - 1815
(2007/10/03)
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- An efficient synthesis of (2S, 6S)- and meso-diaminopimelic acids via asymmetric hydrogenation
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An efficient synthesis of the title compounds 1 and 2 has been successfully developed. The key step is the asymmetric hydrogenation of dehydroamino acid 7 using [Rh(I)(COD)-(S,S) or - (R,R)-Et-DuPHOS)]+OTf- to produce the optically active, protected amino acid derivatives in high ee (>95%). The approach also can be used for the synthesis of other isomers and analogues.
- Wang,Xiong,Yang,Hruby
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- Asymmetric synthesis of differentially protected meso-2,6-diaminopimelic acid
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meso-2,6-Diaminopimelic acid, an important linking component of bacterial cell walls and a biosynthetic precursor of L-lysine has been prepared differentially protected in a stereospecific manner from both L-aspartic and L-glutamic acid. The key step to establish the second chiral center involves the asymmetric reduction of a pyruvate moiety with Alpine-Borane. S-2-Amino-6-oxopimelic acid, the hydrolyzed open chain form of tetrahydrodipicolinic acid, a biosynthetic precursor of meso-2,6-diaminopimelic acid, was also prepared via deprotection of the key pyruvate intermediate.
- Roberts, John L.,Chan, Cecil
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p. 7679 - 7682
(2007/10/03)
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- A concise, stereoselective synthesis of meso-2,6-diaminopimelic acid (DAP)
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The preparation of meso-2,6-diaminopimelic acid 1 is described. The key step in the synthesis is Suzuki coupling of the novel organoboron homoalanine equivalent 3 with methyl (2Z)-3-bromo-2-[(tert-butoxycarbonyl)amino]-2-propenoate 5.
- Collier, Philip N.,Patel, Ian,Taylor, Richard J.K.
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p. 5953 - 5954
(2007/10/03)
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- A simple asymmetric synthesis of (+)- and (-)-2,6-diaminopimelic acids
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The asymmetric synthesis of both the enantiomers of 2,6-diaminopimelic acid (2,6-DAP) has been accomplished starting from the chiral synthon 1. (C) 2000 Elsevier Science Ltd.
- Paradisi,Porzi,Rinaldi,Sandri
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p. 1259 - 1262
(2007/10/03)
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- Stereoselective synthesis of meso-2,6-diaminopimelic acid and its selectively protected derivatives
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Four synthetic routes to selectively protected derivatives and isomers of meso-diaminopimelic acid (DAP) (1a), a key constituent of bacterial peptidoglycan, were investigated. N-(tert-butyloxycarbonyl)-D-allylglycine (2) and N-(benzyloxycarbonyl)-L-allylglycine (4) were esterified to ethylene glycol and cyclized via olefin metathesis to a protected derivative 7 of 2,7- diaminosuberic acid. Analogous linking of propane-1,3-diol with 2 and potential precursors of N-(benzyloxycarbonyl)-L-vinylglycine moieties, such as N-(benzyloxycarbonyl)-L-glutamate or N-(benzyloxycarbonyl)-L-methionine sulfoxide, gave 12 or 15, both of which produced the α,β-unsaturated ester 14 upon attempted generation of the vinylglycine precursor for olefin metathesis to DAP derivatives. An alternative route, based on SnCl4- catalyzed ene reaction of methyl N-(benzyloxycarbonyl)-L-allylglycinate (18) with glyoxylate esters of phenylcyclohexanol isomers as chiral auxiliaries, gave ca. 85:15 ratios of diastereomeric alcohols (19 or 20). These could be transformed to DAP derivatives in a series of steps employing azide displacement of corresponding mesylates to introduce the second nitrogen. A third method, involving reduction of pure dimethyl (6S)-2-keto-6-[N- (benzyloxycarbonyl)amino]pimelate (32) to the corresponding alcohol 33 with (S)-binaphthol-ruthenium catalyst as the key step, gives a 79:21 isomeric ratio. The fourth route employs the bis(oxazoline)-copper complex 41 as a chiral catalyst for the ene reaction of methyl (S)-4- (phenylthio)allylglycinate (39) and methyl glyoxylate to afford 42 and 94:6 isometric ratio. Nickel boride removal of sulfur and the double bond in the presence of the Cbz group gives the desired alcohol, dimethyl (2S,6S)-6-[N- (benzyloxycarbonyl)amino]-2-hydroxyheptane-1,7-dioate (33). The required selectively protected second nitrogen is introduced using Mitsunobu inversion with N-tert-butyl [[2-(trimethylsilyl)-ethyl]sulfonyl]carbomate (34) as a key step.
- Gao, Yong,Lane-Bell, Patricia,Vederas, John C.
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p. 2133 - 2143
(2007/10/03)
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- Stereospecific synthesis of meso-diaminodicarboxylic acids
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The hetero Diels-Alder adducts 1 derived from azodibenzoyl and cyclic dienes were transformed to the meso-diaminodicarboxylic acids 6 via the new cyclic hydrazoacetic acids 3.
- Arakawa,Goto,Kawase,Yoshifuji
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p. 535 - 536
(2007/10/02)
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- Asymmetric Synthesis of 2,6-Diaminopimelic Acids
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The preparations of (R,R)-2,6-diaminopimelic acid, (S,S)-2,6-diaminopimelic acid, (S,R)-2,6-diaminopimelic acid, and (S,S)-2,7-diaminosuberic acid are described.The synthesis of mono-N-protected (S,R)-2,6-diaminopimelic acid is also described.
- Williams, Robert M.,Yuan, Chenguang
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p. 6519 - 6527
(2007/10/02)
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- Synthesis of RP 56142: a New Immunoactive Peptide
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RP 56142, a new immunoactive peptide was synthesized on large scale (ca. 500 g) via L-2,6-diaminopimelic acid which was prepared by chemical or biochemical synthesis.The key derivative, N6-benzyloxycarbonyl-L-2,6-diaminopimelamic acid was synthesized by two methods.In the first, we used a copper chelate procedure.In the second, we selectively deblocked the amine at the α-position to the free carboxylic group by the N-carboxyanhydride method.Condensation of N6-benzyloxycarbonyl-L-2,6-diaminopimelamic acid and the appropriately protected lauroyl dipeptide and removal of the protecting groups afforded RP 56142.
- Bouchaudon, Jean,Dutruc-Rosset, Gilles,Farge, Daniel,James, Claude
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p. 695 - 701
(2007/10/02)
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- Characterization of meso-Diaminopimelate Dehydrogenase from Corynebacterium glutamicum and Its Distribution in Bacteria
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meso-Diaminopimelate dehydrogenase (EC 1.4.1.16) was purified to homogeneity from Corynebacterium glutamicum ATCC 13032.The enzyme had a molecular weight of about 70,000 and consisted of two subunits identical in molecular weight.The enzyme was highly specific for meso-2,6-diaminopimelate.The pH optima for deamination and amination were about 9.8 and 7.9, respectively.The Michaelis contants were 3.1 mM for meso-2,6-diaminopimelate, 0.12 mM for NADP+, 0.28mM for L-2-amino-6-ketopimelate, 36 mM for ammonia, and 0.13 mM for NADPH.D and L isomers of 2,6-diaminopimelate competitively inhibited the oxidative deamination of meso-2,6-diaminopimelate.The enzyme was distributed in a wider range of bacterial species than reported previously when assayed by a sensitive formazan formation method.
- Misono, Haruo,Ogasawara, Masanobu,Nagasaki, Susumu
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p. 2729 - 2734
(2007/10/02)
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- STNTHESIS OF EDEINE ANTIBIOTICS AND THEIR ANALOGS. PART V. ABSOLUTE CONFIGURATION OF 2,6-DIAMINO-7-HYDROXYAZELAIC ACID ISOLATED FROM EDEINES
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Absolute configuration of amino acid component of edeine antibiotics: 2,6-diamino-7-hydroxyazelaic acid was assigned as: (2R,6S,7R) by chemical correlation with (R)-2-aminoadipic and meso-2,6-diaminopimelic acids and 1H NMR and ORD data.
- Gumieniak, Jerzy,Wojciechowska, Hanna,Borowski, Edward
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p. 1519 - 1526
(2007/10/02)
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