Sulfone-stabilized oxosulfonuim ylides

Truce, William E.; Madding, Gary D.

doi:10.1016/s0040-4039(01)99946-0

Cited by 20 publications

(7 citation statements)

References 17 publications

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“…Along with the greater barriers to attack at sulfur(VI), the high polarizability of the chlorine center in -SO 2 Cl and related groups makes it vulnerable to reductive attack (by both one-and two-electron pathways, depending on nucleophile and conditions), so that reactions with carbon nucleophiles usually give mixtures resulting from both sulfonylation and chlorination. 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.…”

Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

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

et al. 2014

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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.

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Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

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

et al. 2014

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“…group and gave l-methyl-3-Pom10-uracil (9), mp 91°, as the major product (50% yield),11 identical with the compound, mp 91°, prepared from 1-methyluracil and chloromethyl pivalate.…”

mentioning

confidence: 81%

“…The first eluted solid (yield 5.6 g, 60%) was recrystallized repeatedly from benzene-ligroin to give dibenzylcyclothymine 5 as colorless prisms: mp 101-103°; uv end absorption with shoulders at 267 nm (<= 400), 263 (650), 257 (1100), 250 (1400); ir (Nujol) 1700 and 1655 cm'1 (NCONCO); nmr (CDClj) 9.40 (1 H, multiplet, H7(endo)), 8.81 (1 H, multiple!, H7(exo>), 7.98 (1 H, multiplet, H5), 7.15 (1 H, multiplet, H6), 5.38 and 5.19 (2 , AB pattern, doublets, J = 15 Hz, C6H-,CH2-), 5.01 (2 H, singlet, CeH .CH,-), 2.69 (10 H, singlet, aromatic protons); mass parent peak at m/e 306.…”

Section: Methodsmentioning

confidence: 99%

“…This oil was treated again with dimethyloxosulfonium methylide under the same conditions. Purification by chromatography on silica gel (benzene-acetone, 10:1) gave l,3-dibenzyl-5-methylcyclothymine 7 as a viscous liquid; yield 0.9 g (58%); ir (Nujol) 1700 and 1660 cm™1 (-CON-CON-); nmr (CDC13) 9.29 (1 H, doublet of doublets, / = 4.5, /' = 6.0 Hz, Hi endo), 9.00 (1 H, triplet, / = 6.0 Hz, H, e,0), 8.73 (3 H, singlet, CH3), 7.31 (1 H, doublets of doublet, / = 4.5, 6.0 Hz, He), 5.29 (2 H, singlet, C6H5CH2), 4.99 (2 H, singlet, C6H5CH2), 2.67 (10 H, singlet, aromatic protons).…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Photo- and stereochemistry of 5,6-methylenepyrimidine nucleosides, bicyclic isomers of thymidine, and 5-methyluridine

Witkop¹,

Kunieda²

1971

J. Am. Chem. Soc.

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Excess dimethyloxosulfonium methylide converted 1,3-dimethyl-or 1,3-dibenzyluracil, 1,3-dibenzylthymine, and 3-methyl-or 3-pivaloyloxymethyl(Pom)-2',3'-0-isopropylidene-5 '-O-trityluridine into the novel 2,4-disubstituted 2,4-diazabicyclo[4.1.0]heptane-3,5-diones which, as ribosides, were separable into diastereoisomers with the 1,6-hydrogens above (ß) and below (a) the plane of the ring in a ratio of 7:3 (3-methyl substituent) or 5:4(3-Pom substituent). The 3-Pom-5,6-methyleneuridines in aqueous alkaline dioxane solution opened up to the corresponding c/s-2-ureidocyclopropane-l-carboxylic acids and as such became separable from the fully protected 3-Pom-uridine starting material. Recyclization with jV-carbethoxy-2-ethoxy-l,3-dihydroquinoline, removal of all blocking groups by acid, and chromatography on silica gel gave l-d-D-ribofuranosyI-5,6-cyclothymine, which on the basis of the positive Cotton effect of the ORD curve was assigned the 1R,6S configuration. Uv irradiation opened

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“…Aufgrund seiner Polarisierbarkeit ist das Chlor in -SO 2 Cl und verwandten Gruppen anfällig für reduktive Angriffe (sowohl durch Ein-als auch Zwei-Elektronen-Reaktionswege, je nach Nukleophil und Reaktionsbedingungen), weswegen Reak-tionen mit Kohlenstoffnukleophilen normalerweise Gemische von sowohl Sulfonierungen als auch Chlorierungen ergeben. Literaturbeispiele umfassen Reaktionen mit Organolithiumreagentien, [27] Schwefelyliden, [28] Phosphoryliden [29] und elektrophile aromatische Substitutionen. [26,30] In all diesen Fällen ergeben Sulfonylfluoride nur Sulfonylierungsergebnisse.…”

Section: Organische Sulfonylfluoride Und Ihre Derivateunclassified

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

et al. 2014

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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.

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Sulfone-stabilized oxosulfonuim ylides

Cited by 20 publications

References 17 publications

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

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

Photo- and stereochemistry of 5,6-methylenepyrimidine nucleosides, bicyclic isomers of thymidine, and 5-methyluridine

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

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