Phosphine-mediated three-component bioconjugation of amino- and azidosaccharides in ionic liquids

Hall, Yvonne; Uzoewulu, Chiamaka Peace; Nizam, Zeinab M.; Ishizawa, Seiya; El-Shaffey, Hisham; Ohata, Jun

doi:10.1039/d2cc04013a

Cited by 7 publications

(6 citation statements)

References 34 publications

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“…Reactions conducted under an atmosphere of 13 CO 2 , in which no 13 C incorporation was observed (Figure S65-S66), ruled out atmospheric CO 2 as the source of the linchpin carbon in the product. [47][48][49][50][51] Regarding the reaction mechanism (Figure 8a), there is scattered precedent for related transformations with mesyl chloride and its derivatives (e.g. 52').…”

Section: Methodsmentioning

confidence: 99%

Selective Macrocyclization of Unprotected Peptides with an Ex Situ Gaseous Linchpin Reagent

Ding,

Pedersen,

Wang

et al. 2024

Angewandte Chemie

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Peptide cyclization has dramatic effects on a variety of important properties, enhancing metabolic stability, limiting conformational flexibility, and altering cellular entry and intracellular localization. The hydrophilic, polyfunctional nature of peptides creates chemoselectivity challenges in macrocyclization, especially for natural sequences without biorthogonal handles. Herein, we describe a gaseous sulfonyl chloride‐derived reagent that achieves amine–amine, amine–phenol, and amine–aniline crosslinking via a minimalist linchpin strategy that affords macrocyclic urea or carbamate products. The cyclization reaction is metal‐mediated, and involves a novel application of sulfine species that remains unexplored in aqueous or biological contexts. The aqueous method delivers unique cyclic or bicyclic topologies directly from a variety of natural bioactive peptides without the need for protecting‐group strategies.

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Section: Methodsmentioning

confidence: 99%

Selective Macrocyclization of Unprotected Peptides with an Ex Situ Gaseous Linchpin Reagent

Ding,

Pedersen,

Wang

et al. 2024

Angewandte Chemie

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“…Despite the undeniable challenges of bioconjugation processes in aqueous media, efforts to discover alternative reaction media that are conducive to both bioconjugation reactions and stabilization of proteins have delivered little. Our research program, termed as Bioconjugation In Nonaqueous-Driven Reaction Solvent (BINDRS), has been pursuing novel bioconjugation technologies in nonaqueous media such as ionic liquids, − and we hypothesized that HFIP would be a suitable candidate as a biomolecule- and organic chemistry reaction-compatible solvent for nonaqueous bioconjugation strategies (Figure A). HFIP and other fluorinated alcohols such as trifluoroethanol have been known to induce a certain secondary structure in peptide (formation of a helicoidal structure) due to their hydrogen-bonding capability, increased acidity of their hydroxyl group, and a high dielectric constant .…”

Section: Introductionmentioning

confidence: 99%

Hexafluoroisopropanol as a Bioconjugation Medium of Ultrafast, Tryptophan-Selective Catalysis

Nuruzzaman,

Colella,

Uzoewulu

et al. 2024

J. Am. Chem. Soc.

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The past decade has seen a remarkable growth in the number of bioconjugation techniques in chemistry, biology, material science, and biomedical fields. A core design element in bioconjugation technology is a chemical reaction that can form a covalent bond between the protein of interest and the labeling reagent. Achieving chemoselective protein bioconjugation in aqueous media is challenging, especially for generally less reactive amino acid residues, such as tryptophan. We present here the development of tryptophan-selective bioconjugation methods through ultrafast Lewis acid-catalyzed reactions in hexafluoroisopropanol (HFIP). Structure−reactivity relationship studies have revealed a combination of thiophene and ethanol moieties to give a suitable labeling reagent for this bioconjugation process, which enables modification of peptides and proteins in an extremely rapid reaction unencumbered by noticeable side reactions. The capability of the labeling method also facilitated radiofluorination application as well as antibody functionalization. Enhancement of an α-helix by HFIP leads to its compatibility with a certain protein, and this report also demonstrates a further stabilization strategy achieved by the addition of an ionic liquid to the HFIP medium. The nonaqueous bioconjugation approaches allow access to numerous chemical reactions that are unavailable in traditional aqueous processes and will further advance the chemistry of proteins.

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“…14 Previously, we reported that an aza-Wittig intermediate (iminophosphorane) can induce amine-azide-CO 2 three-component coupling in ionic liquids to form a stable urea linkage on biomolecules such as peptides/proteins, 15,16 DNAs, 17,18 and saccharides. 19 While other aza-Wittig and Wittig reagents were examined for ionic liquid-based bioconjugation, a Wittig reagent precursor with an aldehyde functional group turned out to be active for condensation reactions with amine groups forming an enamine linkage (Fig. 1A and C).…”

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confidence: 99%

Iron-sensitive protein conjugates formed with a Wittig reaction precursor in ionic liquid

Nizam,

Stowe,

Mckinney

et al. 2023

Chem. Commun.

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Phosphine-mediated three-component bioconjugation of amino- and azidosaccharides in ionic liquids

Abstract: Bioconjugation of carbohydrates have been a challenging task because of their chemical, functional, and structural diversities, and no single chemical modification tool can be universally applicable to all the target...

Cited by 7 publications

References 34 publications

Selective Macrocyclization of Unprotected Peptides with an Ex Situ Gaseous Linchpin Reagent

Selective Macrocyclization of Unprotected Peptides with an Ex Situ Gaseous Linchpin Reagent

Hexafluoroisopropanol as a Bioconjugation Medium of Ultrafast, Tryptophan-Selective Catalysis

Iron-sensitive protein conjugates formed with a Wittig reaction precursor in ionic liquid

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