Über Peptidsynthesen. 11. Mitteilung Intramolekulare Aminoacylwanderung bei Peptiden

Wieland, Theodor; Lang, Hans Ulrich; Liebsch, D.

doi:10.1002/jlac.19555970306

Cited by 21 publications

(3 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The experimental study of the intramolecular S , N -acyl migration reaction occurring from the thioester-linked intermediate would require the isolation of thioesters containing a nucleophilic amino group in their structure. This is potentially difficult due to the high propensity of these compounds to rearrange into amides by S , N -acyl group transfer. ,− The rearrangement can even proceed in relatively acidic conditions as is the case for S -acetylcysteine, which was found to rearrange at pH 3 . Moreover, the monitoring of the rearrangement of S -acyl derivatives of β-aminothiols can potentially be complicated by the fast rate of S , N -acyl migration reactions proceeding through 5-membered ring intermediates.…”

Section: Dissecting the Individual Chemical Steps In Nclmentioning

confidence: 96%

Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations

et al. 2019

View full text Add to dashboard Cite

The native chemical ligation reaction (NCL) involves reacting a C-terminal peptide thioester with an N-terminal cysteinyl peptide to produce a native peptide bond between the two fragments. This reaction has considerably extended the size of polypeptides and proteins that can be produced by total synthesis and has also numerous applications in bioconjugation, polymer synthesis, material science, and micro-and nanotechnology research. The aim of the present review is to provide a thorough mechanistic overview of NCL and extended methods. The most relevant properties of peptide thioesters, Cys peptides, and common solvents, reagents, additives, and catalysts used for these ligations are presented. Mechanisms, selectivity and reactivity are, whenever possible, discussed through the insights of computational and physical chemistry studies. The inherent limitations of NCL are discussed with insights from the mechanistic standpoint. This review also presents a palette of O,S-, N,S-, or N,Se-acyl shift systems as thioester or selenoester surrogates and discusses the special molecular features that govern reactivity in each case. Finally, the various thiol-based auxiliaries and thiol or selenol amino acid surrogates that have been developed so far are discussed with a special focus on the mechanism of long-range N,S-acyl migrations and selective dechalcogenation reactions.

show abstract

Section: Dissecting the Individual Chemical Steps In Nclmentioning

confidence: 96%

Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations

et al. 2019

View full text Add to dashboard Cite

show abstract

“…In contrast, there have been only a few, semi-quantitative investigations of peptide formation from the autocondensation of aminoacyl thioesters (Wieland et al, 1953;Wieland et al, 1955a). We now report the yields of products obtained by the autocondensation of glyS-(Ac-csa) and glySEt at various pH's.…”

Section: Introductionmentioning

confidence: 75%

“…ternately, these unidentified products may have formed via the "aminoacyl insertion reaction" described by Wieland et al (1953) and(1955a).…”

mentioning

confidence: 98%

The formation of peptides from glycine thioesters

Weber

Orgel

1979

J Mol Evol

View full text Add to dashboard Cite

The condensation products obtained from 0.01M S-glycyl-N-acetyl-cysteamine at different pH's were investigated. The highest yields of diketopiperazine (approx. 50%) were observed in phosphate buffers between pH 7.5 and 8.5. The highest yields of diglycine (46%), triglycine (10%) and tetraglycine (2%) were observed in carbonate buffers at pH 9.5. At pH 8.0, over 90% of the glycyl residues of 0.15M S-glycyl-N-acetylcysteamine were incorporated into condensation products, mainly DKP (60--70%). The yields of products from the condensation of S-glycyl-ethanethiol under similar conditions closely resembled those obtained with S-glycyl-N-acetylcysteamine.

show abstract