Journal ArticleDOI
Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry
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
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Journal ArticleDOI
β-Aminosulfonyl Fluorides via Water-Accelerated N-Heterocyclic Carbene Catalysis.
TL;DR: A water-accelerated, N -heterocyclic carbene (NHC)-catalyzed aza-Michael addition reaction to access β-aminosulfonyl fluorides, which are key hubs of the sulfur(VI) fluoride exchange (SuFEx) reaction.
Journal ArticleDOI
The chemistry of ferrocenesulfonyl fluoride revealed.
William Erb,Thierry Roisnel +1 more
TL;DR: The first general route toward polysubstituted ferrocenesulfonyl fluorides was described in this paper, where the authors described a general route towards polysubstantituted Ferrocenes.
Journal ArticleDOI
Design, synthesis, and evaluation of positron emission tomography/fluorescence dual imaging probes for targeting facilitated glucose transporter 1 (GLUT1).
Richard Yuen,Michael Wagner,Susan Richter,Jennifer Dufour,Melinda Wuest,Frederick G. West,Frank Wuest +6 more
TL;DR: In this article, a dual-probe for GLUT1 imaging using positron emission tomography (PET) and fluorescence (Fl) imaging was developed for breast cancer.
Journal ArticleDOI
Fluorosulfonylferrocene, (Trifluoromethylsulfonyl)ferrocene and New Ferrocenyl Sulfonates: Directed ortho Lithiation and New Anionic Thia-Fries Rearrangements at Ferrocene
Journal ArticleDOI
An N-Fluorinated Imide for Practical Catalytic Imidations.
Yuno Oe,Ryuhei Yoshida,Airi Tanaka,Akiya Adachi,Yuichiro Ishibashi,Takashi Okazoe,Kohsuke Aikawa,Takuya Hashimoto +7 more
TL;DR: A novel N-fluorinated imide, N- fluoro-N-(fluorosulfonyl)carbamate (NFC), by which the attached imide moiety acts as a modular synthetic handle for one-step derivatization to amines, sulfonamides, and sulfamides is developed.
References
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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.
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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.
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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.