Palladium–peptide oxidative addition complexes for bioconjugation

Rojas, Anthony J.; Wolfe, Justin M.; Dhanjee, Heemal H.; Buslov, Ivan; Truex, Nicholas L.; Liu, Richard Y.; Massefski, Walter; Pentelute, Bradley L.; Buchwald, Stephen L.

doi:10.1039/d2sc04074c

Cited by 9 publications

(8 citation statements)

References 37 publications

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“…24 Scheme 3 a a (a) Pd(II)-peptide OA complexes synthesized via oxidative addition with 4-iodophenylalanine amino acids. 30 (b) Oligonucleotide OA complexes synthesized via orthogonal NHS ester coupling with aqueous complex. 31 (c) Pd(II)-protein OA complexes synthesized via a Pd(II) rebound process in situ.…”

Section: ■ Chemoselectivitymentioning

confidence: 99%

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Organometallic Oxidative Addition Complexes for S-Arylation of Free Cysteines

Montgomery,

Spokoyny,

Maynard

2024

Bioconjugate Chem.

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Development of bioconjugation strategies to efficiently modify biomolecules is of key importance for fundamental and translational scientific studies. Cysteine S-arylation is an approach which is becoming more popular due to generally rapid kinetics and high chemoselectivity, as well as the strong covalently bonded S-aryl linkage created in these processes. Organometallic approaches to cysteine S-arylation have been explored that feature many advantages compared to their more traditional organic counterparts. In this Viewpoint, progress in the use of Au(III) and Pd(II) oxidative addition (OA) complexes for stoichiometric cysteine S-arylation is presented and discussed. A focus is placed on understanding the rapid kinetics of these reactions under mild conditions, as well as the ability to generate biomolecular heterostructures. Potential avenues for further exploration are addressed and usefulness of these methods to the practitioner are emphasized in the discussion.

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Section: ■ Chemoselectivitymentioning

confidence: 99%

“… a (a) Pd(II)-peptide OA complexes synthesized via oxidative addition with 4-iodophenylalanine amino acids . (b) Oligonucleotide OA complexes synthesized via orthogonal NHS ester coupling with aqueous complex .…”

Section: Benign Reaction Conditionsmentioning

confidence: 99%

Organometallic Oxidative Addition Complexes for S-Arylation of Free Cysteines

Montgomery,

Spokoyny,

Maynard

2024

Bioconjugate Chem.

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“…Within such homogeneous systems, catalytic transformations were primarily perceived through the interactions of organic fragments in the coordination environment of an individual metallic center. The molecular design of catalysts is now appreciated as an influential strategy for the development of both classical transition-metal catalysis − and cutting-edge hybrid methodologies. − …”

Section: Introductionmentioning

confidence: 99%

Revealing Catalyst Self-Adjustment in C–S Cross-Coupling through Multiscale Liquid-Phase Electron Microscopy

Kashin,

Arkhipova,

Sahharova

et al. 2024

ACS Catal.

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Carbon−carbon and carbon−heteroatom bond formation mediated by transition metals is a powerful and convenient methodology for organic synthesis. To effectively meet the demands of catalyst design, an in-depth understanding of the reaction mechanisms and pathways of active species evolution is essential. Advances in electron microscopy now offer unprecedented multilevel visualization of liquid-phase chemical systems, providing a powerful tool for mechanistic studies. In this work, we found that the use of either nickel-or copper-based catalyst precursors with preinstalled thiolate groups in combination with pyridinium ionic liquid as the reaction medium leads to a positive synergistic effect, resulting in the formation of transition metal species with high catalytic activity in the C−S cross-coupling reaction between aryl halides and thiols or disulfides. Through multiscale in situ and operando electron microscopy in the liquid phase, we elucidated the self-adjustment of the catalytic system and revealed the simultaneous emergence of metallic nanoparticles and corresponding thiolate species, leading to the independent activation of the C-and S-substrates and the subsequent elimination of the product via organic group metathesis. The proposed methodology for the catalytic preparation of aromatic organosulfides was used for the design of synthetic routes to pharmacologically important substances.

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“…[8][9][10][11][12] Two-step elaboration of an existing residue to append an electrophile, followed by treatment with a second nucleophilic site is one common approach, but requires careful reagent design. [13][14][15][16] A bifunctional bis-electrophile reagent can be employed in a onestep process, with a suitable linker between reactive groups. [17][18][19][20][21][22] Avoiding multistep manipulations of complex biopolymers is a significant advantage.…”

Section: Introductionmentioning

confidence: 99%

An ex situ gaseous reagent for multicomponent amine bioconjugation

Ding,

Pedersen,

Wang

et al. 2024

Preprint

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Bioconjugation is a large field with many diverse goals, needs, and challenges, that requires a broad toolbox of fundamentally different synthetic approaches. As nucleophilic groups are prevalent in biomolecules, the ability to crosslink two nucleophilic sites offers an attractive approach to construct useful bioconjugates. New technologies for crosslinking with gaseous reagents and with minimal perturbation of natural structure could provide new ways to think about bioconjugation in complex environments. We report a minimalist gaseous sulfonyl chloride-derived reagent for multicomponent bioconjugation with amine, phenol, or aniline reagents to afford urea or carbamate products. In utilizing a gas-phase reagent for a reaction mediated by metal ions, a variety of biologically relevant molecules such as saccharide, PEG, fluorophore, and affinity tag can be efficiently crosslinked to the N-terminus or lysine side chain amines on natural polypeptides or proteins. The application of this method to the production of functional, modified proteins was demonstrated by fluorescence imaging of a cancer cell line and by the facile preparation of a peptide–protein conjugate.

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Palladium–peptide oxidative addition complexes for bioconjugation

Abstract: The synthesis of palladium oxidative addition complexes derived from unprotected peptides is described. Incorporation of 4-halophenylalanine into a peptide during solid phase peptide synthesis allows for subsequent oxidative addition at...

Cited by 9 publications

References 37 publications

Organometallic Oxidative Addition Complexes for S-Arylation of Free Cysteines

Organometallic Oxidative Addition Complexes for S-Arylation of Free Cysteines

Revealing Catalyst Self-Adjustment in C–S Cross-Coupling through Multiscale Liquid-Phase Electron Microscopy

An ex situ gaseous reagent for multicomponent amine bioconjugation

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