A novel protecting group methodology for syntheses using nitroxides

Chalmers, Benjamin A.; Morris, Jason; Fairfull‐Smith, Kathryn E.; Grainger, Richard S.; Bottle, Steven E.

doi:10.1039/c3cc46146g

Cited by 40 publications

(53 citation statements)

References 36 publications

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“…Temporary protection of nitroxides has been achieved previously by reduction and acylation,6 silylation,6a or alkylation7 of the resulting hydroxylamine. Unfortunately, acyl groups are removed by nucleophiles used in oligonucleotide synthesis such as ammonia and methylamine.…”

Section: Resultsmentioning

confidence: 99%

“…Unfortunately, acyl groups are removed by nucleophiles used in oligonucleotide synthesis such as ammonia and methylamine. The recently introduced R 2 N‐O‐CH 3 group requires meta ‐chloroperoxybenzoic acid for demethylation, conditions hardly compatible with oligonucleotides 7. We therefore tested light‐sensitive alkyl groups (Scheme ) 8.…”

Section: Resultsmentioning

confidence: 99%

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Photolabile Protecting Groups for Nitroxide Spin Labels

et al. 2014

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Nitroxide spin labels can be protected against critical conditions of DNA/RNA or peptide synthesis by reduction and alkylation with light‐sensitive groups such as nitrobenzyl‐ or aminocoumarins. High chemical stability qualifies tetraethylisoindoline 5 and, with some restrictions, (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxy (TEMPO) precursor 4 as building blocks for spin‐labeled biopolymers. The yield of recovered nitroxides (80–95 %) is sufficient for PELDOR experiments. A protected TEMPO phosphoramidite was successfully used to synthesize a short spin‐labeled DNA with high yield and purity.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Photolabile Protecting Groups for Nitroxide Spin Labels

et al. 2014

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“…Moreover, we aimed to address nitroxide stability by using a protection strategy. So far, alkylation, silylation, acylation, and photoremovable protecting groups (PPGs) have been demonstrated to protect nitroxides and to release them as needed. In particular, photoirradiation for deprotection is interesting because it enables spatial and temporal control over the release of functional groups.…”

Section: Figurementioning

confidence: 99%

Protein Spin Labeling with a Photocaged Nitroxide Using Diels–Alder Chemistry

et al. 2019

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EPR spectroscopy of diamagnetic bio‐macromolecules is based on site‐directed spin labeling (SDSL). Herein, a novel labeling strategy for proteins is presented. A nitroxide‐based spin label has been developed and synthesized that can be ligated to proteins by an inverse‐electron‐demand Diels–Alder (DAinv) cycloaddition to genetically encoded noncanonical amino acids. The nitroxide moiety is shielded by a photoremovable protecting group with an attached tetra(ethylene glycol) unit to achieve water solubility. SDSL is demonstrated on two model proteins with the photoactivatable nitroxide for DAinv reaction (PaNDA) label. The strategy features high reaction rates, combined with high selectivity, and the possibility to deprotect the nitroxide in Escherichia coli lysate.

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“…This remarkable feature of reversible alkoxyamine switches enables covalent bonding and debonding on demand and has promoted the manufacturing of programmable polymer scaffolds, ranging from refoldable single‐chain polymer nanoparticles to dynamic polymer materials with self‐healing properties . Alkoxyamine dissociation can be triggered through thermolysis, photolysis, or chemically . Recently, electrochemical and electrostatic stimuli have been exploited as alternative external triggers for alkoxyamine fission …”

Section: Methodsmentioning

confidence: 99%

Dynamic Nitroxide Functional Materials

Woehlk

Lauer

Trouillet

et al. 2018

Chemistry A European J

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A substrate‐independent and versatile coating platform for (spatially resolved) surface functionalization, based on nitroxide radical coupling (NRC) reactions and the formation of thermo‐labile alkoxyamine functional groups, was introduced. Nitroxide‐decorated poly(glycidyl methacrylate) (PGMA) microspheres, obtained through bioinspired copolymer surface deposition using dopamine and a nitroxide functional dopamine derivative as monomers, were conjugated with small functional groups in a rewritable process. Reversible coding of the nitroxide functional microspheres by NRC and decoding through thermal alkoxyamine fission were monitored and characterized by electron paramagnetic resonance (EPR) spectroscopy and X‐ray photoelectron spectroscopy (XPS). In addition, this nitroxide coating system was exploited in “grafting‐to” polymer surface ligations of poly(methyl methacrylate) (PMMA) and poly(2,2,2‐trifluoroethyl methacrylate) (PTFEMA) in spatially confined areas. Polymer strands terminated with an Irgacure 2959 (2‐hydroxy‐4′‐(2‐hydroxyethoxy)‐2‐methylpropiophenone) photoinitiator were obtained through chain‐transfer polymerization, and subsequently coupled to nitroxide‐immobilized poly(dopamine) (PDA)‐coated silicon substrates by using rapid photoclick NRC reactions. Light‐driven polymer surface coding was visualized by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and XPS imaging.

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A novel protecting group methodology for syntheses using nitroxides

Cited by 40 publications

References 36 publications

Photolabile Protecting Groups for Nitroxide Spin Labels

Photolabile Protecting Groups for Nitroxide Spin Labels

Protein Spin Labeling with a Photocaged Nitroxide Using Diels–Alder Chemistry

Dynamic Nitroxide Functional Materials

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