Absolute Rate Constants of Alkene Addition Reactions of a Fluorinated Radical in Water

Zhang, L; Wr, Dolbier; Sheeller, Brad; Ku, Ingold

doi:10.1021/ja0256010

Cited by 24 publications

(28 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Next, the failure in scoping simple alkylhalides as reductive carbon radical precursors suggested substrate modulation. α-Fluoro substitution alters the stability and reactivity of the carbon radical 31 and increases the addition reactivity in water 32 . H → F variation might therefore give enhanced RF2C • /RFHC • as near-size 33 RH2C • equivalents, with the potential to generate near-'zero-size' H → F labels in protein side chains.…”

Section: Photocatalytic Carbon Radical Protein Modificationmentioning

confidence: 99%

Light-driven post-translational installation of reactive protein side chains

Josephson

Fehl

Isenegger

et al. 2020

Nature

137

116

View full text Add to dashboard Cite

Post-translational modifications (PTMs) greatly expand the structures and functions of proteins in nature 1,2 . Although synthetic protein functionalization strategies allow mimicry of PTMs 3,4 , as well as formation of unnatural protein variants with diverse potential functions, including drug carrying 5 , tracking, imaging 6 and partner crosslinking 7 , the range of functional groups that can be introduced remains limited. Here we describe the visible-light-driven installation of side chains at dehydroalanine residues in proteins through the formation of carbon radicals that allow C-C bond formation in water. Control of the reaction redox allows site-selective modification with good conversion efficiencies and reduced protein damage. In situ generation of boronic acid catechol ester derivatives generates RH2C • radicals that form the native (β-CH2-γ-CH2) linkage of natural residues and PTMs, whereas in situ potentiation of pyridylsulfonyl derivatives by Fe(II) generates RF2C • radicals that form equivalent β-CH2-γ-CF2 linkages bearing difluoromethylene labels. These reactions are chemically tolerant and incorporate a wide range of functionalities (more than 50 unique residues/side chains) into diverse protein scaffolds and sites. Initiation can be applied chemoselectively in the presence of sensitive groups in the radical precursors, enabling installation of previously incompatible side chains. The resulting protein function and reactivity are used to install radical precursors for homolytic on-protein radical

show abstract

Section: Photocatalytic Carbon Radical Protein Modificationmentioning

confidence: 99%

Light-driven post-translational installation of reactive protein side chains

Josephson

Fehl

Isenegger

et al. 2020

Nature

137

116

View full text Add to dashboard Cite

show abstract

“…Whereas the initial Wittig methylenation was easily accomplished, 15 the allylic bromination step required some optimization (see Supporting Information for details). 16 …”

Section: Resultsmentioning

confidence: 99%

Synthesis of 2,5-Diaryl-1,5-dienes from Allylic Bromides Using Visible-Light Photoredox Catalysis

Pratsch

Overman

2015

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…General Procedure 1 36 . To a flame-dried 100 mL round bottom flask, Ph3PBr (1.2 eq, 4.284 g, 12 mmol) was added.…”

Section: B Preparation Of Olefin Substratesmentioning

confidence: 99%

Synthesis of N-Alkylpyridin-4-ones and Thiazolo[3,2-a]pyridin-5-ones Through Pummerer-Type Reactions

Huang

et al. 2019

Preprint

View full text Add to dashboard Cite

N-alkylated 4-pyridones were obtained through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride activated sulfoxides and 4-fluoropyridine derivatives, followed by hydrolysis. On the other hand, triflic anhydride activated benzyl 6-fluoro-2-pyridyl sulfoxide could react with alkenes or alkynes to afford thiazolo[3,2-a]pyridin-5-ones, via the pyridinium salt intermediates.

show abstract

Absolute Rate Constants of Alkene Addition Reactions of a Fluorinated Radical in Water

Cited by 24 publications

References 21 publications

Light-driven post-translational installation of reactive protein side chains

Light-driven post-translational installation of reactive protein side chains

Synthesis of 2,5-Diaryl-1,5-dienes from Allylic Bromides Using Visible-Light Photoredox Catalysis

Synthesis of N-Alkylpyridin-4-ones and Thiazolo[3,2-a]pyridin-5-ones Through Pummerer-Type Reactions

Contact Info

Product

Resources

About