Phenylthiocarbamate or<i>N</i>-Carbothiophenyl Group Chemistry in Peptide Synthesis and Bioconjugation

Melnyk, Oleg; Ollivier, Nathalie; Besret, Soizic; Melnyk, Patricia

doi:10.1021/bc500052r

Cited by 8 publications

(6 citation statements)

References 109 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our approach to create oxazolines for PPM was inspired by biological studies showing that thiocarbamate-based pesticides are oxidized to the sulfinyl or sulfonyl species in cells, upon which they act as potent S -carbamoylating agents. − As a result, we set out to create similar structures by the CROP of a 2-alkylthio-2-oxazoline (Figure c). We hypothesized that the alkylthio side chain would suppress chain transfer processes relative to the alkoxy side chain owing to the diminished driving force of the ensuing CS vs CO bond formation.…”

mentioning

confidence: 99%

Living Polymerization of 2-Ethylthio-2-oxazoline and Postpolymerization Diversification

Swager

2019

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The postpolymerization modification of polymers produced by living polymerization is an attractive method to create precision nanomaterials. We describe the living cationic ring-opening polymerization of a 2-alkylthio-2-oxazoline to furnish a polythiocarbamate. The polythiocarbamate is activated toward substitution by N - and S -nucleophiles via oxidation of the S to an SO 2 . Mild substitution conditions provide broad functional group tolerance, constituting a versatile postpolymerization modification platform with access to a diversity of polyureas and polythiocarbamates. We further demonstrate the utility of this strategy by synthesizing and functionalizing block copolymers.

show abstract

mentioning

confidence: 99%

Living Polymerization of 2-Ethylthio-2-oxazoline and Postpolymerization Diversification

Swager

2019

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…39,40 However, thiophenol is toxic and malodorous and requires an extraction procedure prior to the RP-HPLC purification step. Thus, we examined the possibility of performing the ligation in the absence of thiophenol to facilitate the preparation of the conjugates.…”

Section: Resultsmentioning

confidence: 99%

“…The principle of the thiocarbamate ligation 39 , 40 is presented in Figure 1 C. The process is based on the reaction of a thiol such as a peptide featuring a cysteine residue with a phenylthiocarbamate (PTC) component. It is formely a thiol–thioester exchange which proceeds efficiently in water at neutral pH.…”

Section: Resultsmentioning

confidence: 99%

“…The procedure initially described for thiocarbamate ligation used thiophenol as an additive to minimize the oxidation of cysteine residues. , However, thiophenol is toxic and malodorous and requires an extraction procedure prior to the RP-HPLC purification step. Thus, we examined the possibility of performing the ligation in the absence of thiophenol to facilitate the preparation of the conjugates.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Thiocarbamate-Linked Polysulfonate–Peptide Conjugates As Selective Hepatocyte Growth Factor Receptor Binders

et al. 2014

Self Cite

View full text Add to dashboard Cite

The capacity of many proteins to interact with natural or synthetic polyanions has been exploited for modulating their biological action. However, the polydispersity of these macromolecular polyanions as well as their poor specificity is a severe limitation to their use as drugs. An emerging trend in this field is the synthesis of homogeneous and well-defined polyanion–peptide conjugates, which act as bivalent ligands, with the peptide part bringing the selectivity of the scaffold. Alternately, this strategy can be used for improving the binding of short peptides to polyanion-binding protein targets. This work describes the design and first synthesis of homogeneous polysulfonate–peptide conjugates using thiocarbamate ligation for binding to the extracellular domain of MET tyrosine kinase receptor for hepatocyte growth factor.

show abstract

“…Many of these methods make use of the nucleophilic properties of peptide side chains, in particular cysteine . Less common are methods to conjugate nucleophiles to electrophilic peptides …”

mentioning

confidence: 99%

C-Terminal Modification of Fully Unprotected Peptide Hydrazides via in Situ Generation of Isocyanates

2016

View full text Add to dashboard Cite

A method for chemo- and regioselective conjugation of nucleophiles to fully unprotected peptides and proteins via in situ generation of C-terminal isocyanates is reported. Oxidation of C-terminal peptide hydrazides in aqueous media followed by Curtius rearrangement of acyl azides reliably generates isocyanates, which react with a variety of external nucleophiles, such as hydrazines, hydrazides, aromatic thiols, and hydroxylamines. Multiple peptides and a 53 kDa protein hydrazide were conjugated to different nucleophiles using this reaction.

show abstract

Phenylthiocarbamate orN-Carbothiophenyl Group Chemistry in Peptide Synthesis and Bioconjugation

Cited by 8 publications

References 109 publications

Living Polymerization of 2-Ethylthio-2-oxazoline and Postpolymerization Diversification

Living Polymerization of 2-Ethylthio-2-oxazoline and Postpolymerization Diversification

Thiocarbamate-Linked Polysulfonate–Peptide Conjugates As Selective Hepatocyte Growth Factor Receptor Binders

C-Terminal Modification of Fully Unprotected Peptide Hydrazides via in Situ Generation of Isocyanates

Contact Info

Product

Resources

About