Protected Amino Acids in Peptide Synthesis

Meienhofer, Johannes

doi:10.1007/978-94-009-4832-7_9

Cited by 8 publications

(4 citation statements)

References 285 publications

(209 reference statements)

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“…Moreover, it has been reported 39 that chiral discrimination exists between amino acids. The butoxycarbonyl (BOC) amino acids, often used in peptide synthesis, were of great interest because they bear a bulky tert -butyl group that can lead to a large steric hindrance with the amino acids and an extra carboxyl group that can result in increased hydrogen bonding with the amino acids.…”

Section: Resultsmentioning

confidence: 99%

Chiral Analysis by Electrospray Ionization Mass Spectrometry/Mass Spectrometry. 1. Chiral Recognition of 19 Common Amino Acids

et al. 2000

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Chiral recognition of 19 common amino acids was achieved by investigating the collision-induced dissociation spectra of protonated trimers that were formed from the electrospray ionization of amino acids in the presence of one of the following chiral selectors: L- or D-N-tert-butoxycarbonylphenylalanine, L- or D-N-tert-butoxycarbonylproline, and L- or D-N-tert-butoxycarbonyl-O-benzylserine. The protonated trimers were dissociated to protonated dimers, and the intensity ratios of the protonated dimer (product ion) to the protonated trimer (precursor ion), i.e., the observed dissociation efficiency, was found to be strongly dependent on the chirality of the amino acids with respect to that of the chiral selectors. The results showed that the chirality of all 19 common amino acids can be definitely differentiated. The method was demonstrated as rapid, sensitive, precise, robust, and requiring no reference standards and only minimal sample preparation. The chirality of all three amino acids in a mixture was determined without prior separation of the amino acids, consuming only 70 pmol of sample and requiring only approximately 14 min of mass spectrometric measurements. A cyclodipeptide with unknown chirality was determined to be cyclo-(L-Pro-L-Leu) by acid hydrolysis followed by the present method, and the results were consistent with the physiochemical properties and NMR data of the compound. This study suggested that ESI-MS/MS can be a promising approach for the chiral recognition of other compounds.

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Section: Resultsmentioning

confidence: 99%

Chiral Analysis by Electrospray Ionization Mass Spectrometry/Mass Spectrometry. 1. Chiral Recognition of 19 Common Amino Acids

et al. 2000

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“…[2][3][4] α-AAs have been one of the most common and important chiral molecules to sustain life, that inspired organic chemists to spend considerable efforts mimicking functions found in nature. [5][6][7] α-AAs have been categorized into four forms on the basis of properties of their side chains, amino acids with electrically charged side chains, amino acids with polar uncharged side chains, amino acids with hydrophobic side chains and special cases (Figure 1). To explore the α-amino acid as chiral synthon, our group has reported some research articles [8][9][10][11][12][13][14][15][16][17] and reviews [18][19][20] on αamino acids.…”

Section: Introductionmentioning

confidence: 99%

Use of Non‐Aromatic Hydrophobic α‐Amino Acids (α‐AA) and Non‐Amino Acid Derived Synthons: Comparative Studies Towards Total Syntheses of Selected Bioactive Natural Alkaloids

et al. 2022

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the total synthesis of selected natural alkaloids have been compared based on atom economy, overall chemical yield, stereoselectivity and sustainability with cost effective manner by using inexpensive commercially available starting materials but the source of chiral pool mainly α-amino acids to target natural alkaloids in chiral synthesis will be playing an important role. In selected cases of alkaloids synthesized from non-amino acid route, an external chiral source of induction like metal and organometallic catalysts to generate chirality in the molecule are used.

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“…N-tert-Butoxycarbonyl (Boc) group is one of the most common amino protecting groups as well as N-Z group in the field of amino acid chemistry. 15) However, it is impossible to use the N-Boc group in our phospho- nylation under a Lewis acid catalyst. Therefore, we tried a conversion of the N-Z products into the N-Boc derivatives by the method developed for that of a-amino acids.…”

mentioning

confidence: 99%

“…Deprotection of the N-protecting groups by the appropriate procedure utilizing in amino acid chemistry 15,17) and hydrochloric acidcatalyzed hydrolysis of the methyl phosphonate moieties followed by desalting to the salt-free aminophosphonic acids were successfully achieved. The structure of target compounds (9, 10) was supported by their analytical and spectral data, which were in accordance with literature data of the compounds (9, 10) synthesized from a different non-amino acids source.…”

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confidence: 99%

Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.

Kaname¹,

Mashige

Yoshifuji

2001

Chem. Pharm. Bull.

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a-Aminophosphonic acids are believed to be phosphorus analogs of naturally occurring a-amino acids and have found applications as potent active compounds with a wide range of biological activities as antibiotics, 1) enzyme inhibitors,2) pharmacological agents, 2b,3) antiviral agents, 4) and herbicides.5) Their negligible mammalian toxicity, and the fact that they bear a very close chemical resemblance to their amino carboxylic counterparts, make them remarkably important structural units of phosphonopeptides and peptidomimetics.6) During the last two decades, considerable efforts toward the synthesis of a-aminophosphonic acids have been made. 7) However, a simple and general synthetic method for cyclic amino-type of compounds, such as phosphonic acid analogs of 2-pyrrolidinecarboxylic acid (proline) and 2-piperidinecarboxylic acid, is not relatively known, and most of the reported methods are about acyclic compounds. The cyclic analogues can be viewed as useful tools for the elucidation of conformational requirements of a receptor, since the conformation is easily fixed. Many synthetic routes to a-aminophosphonic acids and their derivatives include a key step of nucleophilic phosphonylation to either performed or in situ generated imines (Schiff bases) or iminium ions. 8)Shono 9) and co-workers reported the phosphonylation of Nprotected 2-methoxyamines using trialkyl phosphites in the presence of Lewis acids. Similar transformation of 2-benzotriazolylpyrrolidine derivatives into pyrrolidine-2-phosphonic acid esters was reported by Katritzky 10) and co-workers. We wish to report herein the convenient conversion of cyclic aamino acids to cyclic a-aminophosphonic acids through the corresponding N-protected 2-hydroxyamines, with which easy generation of acyliminium ions in the presence of Lewis acids would be expected. To our knowledge, only a few studies concerning the chemical conversion of naturally occurring cyclic a-amino acid (proline or proline-containing dipeptide) into the corresponding phosphonic acid analogues have been published, 11,12) and these are not systematic or detailed studies. In this paper, we describe a systematic study on a simple route to a series of phosphonic acid analogues from proline and 2-piperidinecarboxylic acid, as illustrated in Chart 1.Initially, we examined the transformation of commercially available cyclic a-amino acids (1, 2) into the key intermediates of cyclic N-protected 2-hydroxyamines (5, 6). Displacement of the carboxylic acid moiety by hydroxy group or its equivalents such as acetoxy group had been realized by using two methods of oxidative decarboxylation: lead tetraacetate [Pb(OAc) 4 ] oxidation 13) of carboxylic acids and m-chloroperbenzoic acid (m-CPBA) oxidation 14) of active esters. We applied these methods to N-protected amino acids (3a-e, 4a-c) and their active esters (3f, g), as summarized in Table1. L-Proline derivatives (3a-e) having various N-protecting groups were oxidized with Pb(OAc) 4 to the desired 2-hydroxy compounds (5a-e) in good yields. N-Benzoyl (B...

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Protected Amino Acids in Peptide Synthesis

Cited by 8 publications

References 285 publications

Chiral Analysis by Electrospray Ionization Mass Spectrometry/Mass Spectrometry. 1. Chiral Recognition of 19 Common Amino Acids

Chiral Analysis by Electrospray Ionization Mass Spectrometry/Mass Spectrometry. 1. Chiral Recognition of 19 Common Amino Acids

Use of Non‐Aromatic Hydrophobic α‐Amino Acids (α‐AA) and Non‐Amino Acid Derived Synthons: Comparative Studies Towards Total Syntheses of Selected Bioactive Natural Alkaloids

Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.

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