Journal ArticleDOI
Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry
Reads0
Chats0
TLDR
It is shown that proton or silicon centers can activate the exchange of S�F bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis.Abstract:
Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.read more
Citations
More filters
Journal ArticleDOI
Late-stage fluorination: fancy novelty or useful tool?
TL;DR: It is outlined how an improved understanding of the bonding interactions of fluoride could lead to a new class of mild fluorinating reagents and a range of functional-group-tolerant reactions.
Journal ArticleDOI
Dendrimers: A versatile nanocarrier for drug delivery and targeting.
TL;DR: The present review provide a comprehensive outline of synthesis of dendrimers, interaction of d endrimer with guest molecules, properties, characterization and their potential applications in pharmaceutical and biomedical field.
Journal ArticleDOI
PyFluor: A Low-Cost, Stable, and Selective Deoxyfluorination Reagent
TL;DR: An inexpensive, thermally stable deoxyfluorination reagent is reported that fluorinates a broad range of alcohols without substantial formation of elimination side products and enables deoxy fluorination on preparatory scale.
Journal ArticleDOI
Bifluoride-catalysed sulfur( VI ) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates
Bing Gao,Linda Zhang,Qinheng Zheng,Feng Zhou,Liana M. Klivansky,Jianmei Lu,Yi Liu,Jiajia Dong,Peng Wu,K. Barry Sharpless +9 more
TL;DR: The bifluoride salts are significantly more active in catalysing the SuFEx reaction compared to organosuperbases, therefore enabling much lower catalyst-loading and the process is practical with regard to the reduced cost of catalyst, polymer purification and by-product recycling.
Journal ArticleDOI
Arylfluorosulfates Inactivate Intracellular Lipid Binding Protein(s) through Chemoselective SuFEx Reaction with a Binding Site Tyr Residue
Wentao Chen,Jiajia Dong,Lars Plate,David E. Mortenson,Gabriel J. Brighty,Suhua Li,Yu Liu,Andrea Galmozzi,Peter Lee,Jonathan J. Hulce,Benjamin F. Cravatt,Enrique Saez,Evan T. Powers,Ian A. Wilson,K. Barry Sharpless,Jeffery W. Kelly +15 more
TL;DR: It is discovered that simple hydrophobic arylfluorosulfates selectively react with a few members of the intracellular lipid binding protein (iLBP) family and can selectively target single iLBPs, making them useful for understanding iLBP function.
References
More filters
Journal ArticleDOI
A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes.
Journal ArticleDOI
Click Chemistry: Diverse Chemical Function from a Few Good Reactions.
TL;DR: In this paper, a set of powerful, highly reliable, and selective reactions for the rapid synthesis of useful new compounds and combinatorial libraries through heteroatom links (C-X-C), an approach called click chemistry is defined, enabled, and constrained by a handful of nearly perfect "springloaded" reactions.
Journal ArticleDOI
Peptidotriazoles on solid phase: [1,2,3]-triazoles by regiospecific copper(i)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides.
TL;DR: A novel regiospecific copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes to azides on solid-phase is reported, and the X-ray structure of 2-azido-2-methylpropanoic acid has been solved, to yield structural information on the 1, 3-dipoles entering the reaction.
Journal ArticleDOI
1,3-Dipolar Cycloadditions. Past and Future†
TL;DR: In contrast to the very large number of special methods applicable to syntheses in the heterocyclic series, relatively few general methods are available as discussed by the authors, and the 1,3-dipolar addition offers a remarkably wide range of utility in the synthesis of five-membered heterocycles.
Journal ArticleDOI
A Strain-Promoted [3 + 2] Azide−Alkyne Cycloaddition for Covalent Modification of Biomolecules in Living Systems
TL;DR: A strain-promoted [3 + 2] cycloaddition between cyclooctynes and azides that proceeds under physiological conditions without the need for a catalyst was demonstrated by selective modification of biomolecules in vitro and on living cells, with no apparent toxicity.