Zur Kenntnis der <i>o</i>‐Chinone, XVI. Additionsreaktionen mit 3‐Methoxy‐<i>o</i>‐chinon

Horner, L.; Göwecke, Siegfried

doi:10.1002/cber.19610940516

Cited by 26 publications

(7 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Examples from the literature include reactions with organolithium reagents, [27] sulfur ylides, [28] phosphorous ylides, [29] and electrophilic aromatic substitution. [26,30] In all these cases, sulfonyl fluorides provide only sulfonylation outcomes. The same reasoning applies to the use of sulfonimidoyl fluorides over parent chlorides.…”

Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

View full text Add to dashboard Cite

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 SF bonds for SO 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.

show abstract

Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

View full text Add to dashboard Cite

show abstract

“…The sulfoxides and sulfones were obtained at a high yield by oxidation of sulfides with m -CPBA. 13 The preparation of compounds 10 and 16 was reported in the literature, 14–16 but neither of the compounds were synthesized by the procedures described here, nor were they examined for potential cytotoxic and antitubulin activities. The structure of all compounds was confirmed by spectroscopic methods.…”

Section: Resultsmentioning

confidence: 99%

“…65.5–66.5 °C). 14 IR (KBr) ν max /cm −1 : 3093 (aromatic CH), 2842 (methyl CH), 1581 (C=C), 1303, 1145 (S=O), 1095 (C-O). 1 H NMR (CDCl 3 ) δ (ppm): 3.75 (s, 3H, OCH 3 ), 3.79 (s, 3H, OCH 3 ), 3.92 (s, 3H, OCH 3 ), 6.77 (d, J = 8.9 Hz, 1H, Ar-H), 7.53 (m, 3H, Ar-H), 7.87 (d, J = 8.9 Hz, 1H, Ar-H), 7.95 (d, J = 7.2 Hz, 2H, Ar-H).…”

Section: Methodsmentioning

confidence: 99%

Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

Santos¹,

Prado²,

Carvalho³

et al. 2013

Quím. Nova

View full text Add to dashboard Cite

We extended our previous exploration of sulfur bridges as bioisosteric replacements for atoms forming the bridge between the aromatic rings of combretastatin A-4. Employing coupling reactions between 5-iodo-1,2,3-trimethoxybenzene and substituted thiols, followed by oxidation to sulfones with m-CPBA, different locations for attaching the sulfur atom to ring A through the synthesis of nine compounds were examined. Antitubulin activity was performed with electrophoretically homogenous bovine brain tubulin, and activity occurred with the 1,2,3-trimethoxy-4-[(4-methoxyphenyl)thio]benzene (12), while the other compounds were inactive. The compounds were also tested for leishmanicidal activity using promastigote forms of Leishmania braziliensis (MHOM/BR175/M2904), and the greatest activity was observed with 1,2,3-trimethoxy-4-(phenylthio)benzene (10) and 1,2,3-trimethoxy-4-[(4-methoxyphenyl) sulfinyl]benzene (15).

show abstract

“…Literaturbeispiele umfassen Reaktionen mit Organolithiumreagentien, [27] Schwefelyliden, [28] Phosphoryliden [29] und elektrophile aromatische Substitutionen. [26,30] In all diesen Fällen ergeben Sulfonylfluoride nur Sulfonylierungsergebnisse. Gleiches gilt für die Reaktivität von Sulfonimidoylfluoriden im Vergleich zu den Chloriden.…”

Section: Organische Sulfonylfluoride Und Ihre Derivateunclassified

Schwefel(VI)‐fluorid‐Austausch (SuFEx): Eine weitere gute Anwendung für die Click‐Chemie

et al. 2014

View full text Add to dashboard Cite

Arylsulfonylchloride (z. B. Ts‐Cl) sind die am häufigsten eingesetzten SVI‐Elektrophile in der organischen Synthesechemie, und auch die Stammverbindung, das Sulfurylchlorid (O2SVICl2), wurde zur Synthese von Sulfaten und Sulfamiden genutzt. Allerdings wird die gewünschte Halogenidsubstitution oftmals durch die Zersetzung des Schwefelelektrophils in SIV‐Spezies und Cl− verhindert, denn die SVI‐Cl‐Bindung ist äußerst reduktionsanfällig. Mit Schwefel(VI)‐fluoriden (z. B. R‐SO2‐F und SO2F2) verläuft die Umsetzung hingegen ausschließlich über den Substitutionsweg. Wie es bei der Click‐Chemie zumeist der Fall ist, wurden viele entscheidende Aspekte der Reaktivität von Schwefel(VI)‐fluoriden vor langer Zeit in Deutschland entdeckt.6a Überraschenderweise gerieten diese außerordentlichen Arbeiten in der Mitte des 20. Jahrhunderts ziemlich abrupt aus dem Blickfeld. In diesem Aufsatz versuchen wir, dieser Chemie neues Leben einzuhauchen. Insbesondere stützen wir uns dabei auch auf John Hyatts unbeachtet gebliebene Veröffentlichung über CH2CH‐SO2‐F aus dem Jahr 1979.98 Wir tragen mehrere neue Beobachtungen bei, einschließlich dem Befund, dass das ansonsten sehr stabile Gas SO2F2 eine exzellente Reaktivität unter den richtigen Umständen aufweist. Wir zeigen auch, dass Protonen oder Siliciumzentren den Austausch von S‐F‐Bindungen gegen S‐O‐Bindungen aktivieren können und dass der Sulfat‐Konnektor überraschend hydrolysestabil ist. Anwendungen dieser kontrollierbaren Ligationschemie auf kleine Moleküle, Polymere und Biomoleküle werden diskutiert.

show abstract

Zur Kenntnis der o‐Chinone, XVI. Additionsreaktionen mit 3‐Methoxy‐o‐chinon

Cited by 26 publications

References 19 publications

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

Schwefel(VI)‐fluorid‐Austausch (SuFEx): Eine weitere gute Anwendung für die Click‐Chemie

Contact Info

Product

Resources

About