- Manganese(iii) acetate-mediated direct C(sp2)-H-sulfonylation of enamides with sodium and lithium sulfinates
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A Mn(OAc)3 mediated oxidative C(sp2)-H sulfonylation of enamides and encarbamates with sodium and lithium sulfinates is reported. This operationally simple transformation provides a straightforward and highly stereoselective access to (E)-β-amidovinyl sulfones in moderate to excellent yields. The reaction proceeds readily under mild conditions at room temperature and tolerates various sensitive functional groups. This process affords exclusively (E)-configurated β-amidovinyl sulfones independent of the starting material configuration. Moreover, a direct transformation of organolithium reagents and sulfur dioxide into β-amidovinyl sulfones is described.
- Kramer, Philipp,Krieg, Sara-Cathrin,Kelm, Harald,Manolikakes, Georg
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- Copper-Mediated Sulfonylation of Aryl C(sp2)-H Bonds with Sodium and Lithium Sulfinates
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A copper-mediated direct sulfonylation of aryl C(sp2)-H bonds with sodium and lithium sulfinates is reported. Various aryl sulfones were synthesized in moderate to excellent yields with good functional group tolerance.
- Liang, Shuai,Liu, Nai-Wei,Manolikakes, Georg
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- Nickel(II)-Catalyzed Synthesis of Sulfinates from Aryl and Heteroaryl Boronic Acids and the Sulfur Dioxide Surrogate DABSO
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We report a redox-neutral Ni(II)-catalyzed sulfination of readily available aryl and heteroaryl boronic acids. Using the combination of commercially available, air-stable NiBr2·(glyme), a commercially available phenanthroline ligand, and DABSO, boronic acids are efficiently converted to the corresponding sulfinate salts, which can be further elaborated to valuable sulfonyl-containing groups, including sulfones, sulfonamides, sulfonyl fluorides, and sulfonate esters. The catalyst loading can be reduced to 2.5 mol ?% on a gram scale. This practically simple protocol tolerates an unprecedented range of pharmaceutically relevant and electron-poor (hetero)aryl boronic acids, allowing the direct synthesis of active pharmaceutical ingredients.
- Lo, Pui Kin Tony,Chen, Yiding,Willis, Michael C.
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p. 10668 - 10673
(2019/11/11)
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- Copper-Catalyzed Remote para-C?H Functionalization of Anilines with Sodium and Lithium Sulfinates
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A copper-catalyzed, cross-dehydrogenative coupling of anilines with sodium and lithium sulfinates was developed. By using a cooperative reaction system with Mn(OAc)3as stoichiometric co-oxidant a highly selective para-functionalization of anilines was accomplished. Various functional groups were tolerated and the desired products were obtained in high yields. This method not only provides a novel approach for the synthesis of arylsulfones but might also offer new opportunities for the development of copper-catalyzed para-selective C?H functionalizations.
- Liang, Shuai,Bolte, Michael,Manolikakes, Georg
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supporting information
p. 96 - 100
(2017/01/09)
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- Manganese(III) Acetate Mediated C–H Sulfonylation of 1,4-Dimethoxybenzenes with Sodium and Lithium Sulfinates
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A simple and mild Mn(OAc)3-promoted oxidative coupling of 1,4-dimethoxybenzenes with sodium and lithium sulfinates was developed. The reaction proceeded readily at room temperature in air, and various sulfones were synthesized in moderate to high yields. In addition, a straightforward approach for the conversion of organolithium reagents and sulfur dioxide into sulfonylated 1,4-dimethoxybenzenes was explored.
- Liang, Shuai,Ren, Yueling,Manolikakes, Georg
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supporting information
p. 4117 - 4120
(2017/08/07)
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- Copper-Catalyzed Remote C?H Functionalization of 8-Aminoquinolines with Sodium and Lithium Sulfinates
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A simple and mild copper-catalyzed sulfonylation of 8-aminoquinolines with sodium and lithium sulfinates is reported. In the presence of manganese(III) acetate [Mn(OAc)3] as cooxidant a highly site-selective C?H functionalization at the C-5 position takes place. The reaction proceeds readily at room temperature in air and various sulfones were synthesized in moderate to high yields. Moreover, a straightforward procedure for the conversion of organolithium reagents and sulfur dioxide into C-5 sulfonylated quinolines was developed. (Figure presented.).
- Liang, Shuai,Manolikakes, Georg
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supporting information
p. 2371 - 2378
(2016/08/16)
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- One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts
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A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.
- Margraf, Natalie,Manolikakes, Georg
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p. 2582 - 2600
(2015/03/18)
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- Arylation of lithium sulfinates with diaryliodonium salts: A direct and versatile access to arylsulfones
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An efficient, transition-metal-free arylation of lithium sulfinates, which are readily accessible from reactions of organolithium reagents with sulfur dioxide, is described. Based on this method, a practical protocol for the direct transformation of (hetero)arenes and (hetero)aromatic halides into diarylsulfones was developed.
- Umierski, Natalie,Manolikakes, Georg
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supporting information
p. 4972 - 4975
(2013/10/22)
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- Synthesis and characterization of lithium oxonitrate (LiNO)
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The oxonitrate(1 -) anion (NO-), the one-electron reduction product of nitric oxide and conjugate base of HNO, has not been synthesized and isolated due to the inherent reactivity of this anion. The large scale synthesis and characterization of a stable NO- salt is described here. The lithium salt of oxonitrate (LiNO) was formed by the deprotonation of N-hydroxybenzenesulfonamide with phenyllithium in aprotic, deoxygenated conditions. LiNO exhibited antiferromagnetic paramagnetism as determined by SQUID magnetometry, consistent with a triplet ground state of NO-. LiNO reacted with HCl to yield nitrous oxide consistent with HNO formation and dimerization. LiNO consumed O2 in a pH-dependent manner to initially produce peroxynitrite and eventually nitrite. Consistent with the reduction potential of NO, LiNO exhibited an oxidation potential of approximately + 0.80 V as determined by reactions with a series of viologen electron acceptors. LiNO also reacted with ferric tetraphenylporphyrin chloride (Fe(TPP)Cl), potassium tetracyanonickelate (K2Ni(CN)4) and nitrosobenzene in a manner that is identical to other HNO/NO- donors. We conclude that the physical and chemical characteristics of LiNO are indistinguishable from the experimentally and theoretically derived data on oxonitrate (1 -) anion. The bulk synthesis and isolation of a stable 3NO- salt described here allow the chemical and physical properties of this elusive nitrogen oxide to be thoroughly studied as this once elusive nitrogen oxide is now attainable.
- Switzer, Christopher H.,Miller, Thomas W.,Farmer, Patrick J.,Fukuto, Jon M.
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p. 128 - 133
(2013/02/23)
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- Oxidation of aromatic lithium thiolates into sulfinate salts: An attractive entry to aryl sulfones labeled with carbon-11
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Aromatic 11C-sulfones were synthesized by S alkylation of lithium arenesulfinates, which are readily available from the corresponding thiols by an oxaziridine-mediated oxidation reaction with [11C]alkyl iodides in THF/H2O (4:1) at 150 °C. The radiosyntheses, including purification by HPLC, were completed in an average of 35 min from the end of the bombardment with 55-76% overall radiochemical yields (decay corrected). The described procedure extends the range of accessible labeling methods.
- Martin, Claudie,Sandrinelli, Franck,Perrio, Cecile,Perrio, Stephane,Lasne, Marie-Claire
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p. 210 - 214
(2007/10/03)
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- Unexpected differences in the α-halogenation and related reactivity of sulfones with perhaloalkanes in KOH-t-BuOH
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Most alkyl phenyl sulfones are readily α-chlorinated with CCl4 and α-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily α-chlorinated with CCl4, it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting α-anion formation. This effect is reversed by the electron-withdrawing influence of two α-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily α-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the α-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the α-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-α-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that α,α-dihalogenation is attained while much substrate is still present and the mono-α-halogenated product is not detected. The ease of reductive debromination of α-bromo sulfones with Cl3C- was correlated with the stability of the formed α-anions, explaining the success with α-bromobenzylic sulfones but failure with α-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the α-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes.
- Meyers, Cal Y.,Chan-Yu-King, Roch,Hua, Duy H.,Kolb, Vera M.,Matthews, Walter S.,Parady, Thomas E.,Horii, Toyokazu,Sandrock, Paul B.,Hou, Yuqing,Xie, Songwen
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p. 500 - 511
(2007/10/03)
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- Oxidation of thiolates with oxaziridines: An efficient method to the preparation of sulfoxides, sulfones and sulfonic acid derivatives
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Oxaziridine-mediated oxidation reactions of thiolates into sulfenates and sulfinates are reported.
- Sandrinelli, Franck,Perrio, Stephane,Beslin, Pierre
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p. 381 - 382
(2007/10/03)
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- A new reaction of 2-(phenylsulfonyl)-3-phenyloxaziridine (davis reagent): Oxidation of thiolates to sulfinates. Application to the synthesis of sulfones
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(Matrix Presented) The first efficient and general method for the generation of sulfinate anions by oxidation of the corresponding thiolates is described. The oxidizing agent employed is the classical 2-(phenylsulfonyl)-3-phenyloxaziridine, commonly known as the Davis reagent. Subsequent S-alkylation of the sulfinates under phase-transfer catalysis affords sulfones 6 in 71-91% isolated yields (10 examples).
- Sandrinelli, Franck,Perrio, Stephane,Beslin, Pierre
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p. 1177 - 1180
(2008/02/09)
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- STEREOCONTROLLED SYNTHESIS OF A C14-C20 BUILDING BLOCK FOR AMPHOTERICIN B USING A NOVEL WITTIG REARRANGEMENT
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The C14-C20 unit 11 of the polyene macrolide antibiotic amphotericin B (1) was synthesized from L-arabinose in 13 steps.The key step 7 -> 10 features diastereocontrol through asymmetric induction in a novel Wittig rearrangement.
- Bruecker, Reinhard
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p. 5747 - 5750
(2007/10/02)
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- THIOSULFONIC S-ESTERS-III. A CONVENIENT PREPARATION OF AROMATIC SULFIDES
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The nucleophilic attack of alkyl- and aryl-lithium compounds at the sulfenyl sulfur atom in thiosulfonic S-esters performs a convenient synthesis of aromatic sulfides which are obtained cleanly and in generally excellent yields.Considering that recently we have reported a ready preparation of thiosulfonic S-esters from sulfonyl chlorides, this sulfidation reaction completes an interesting general procedure for converting the laters to any symmetrical or unsymmetrical sulfides.
- Palumbo, Giovanni,Ferreri, Carla,D'Ambrosio, Clotilde,Caputo, Romualdo
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p. 235 - 238
(2007/10/02)
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- Studies on the Occurence of Hydrogen Transfer. 65. The Significance of Solvents and Solvent Mixtures in the Reductive Cleavage of Compounds of the Type ArSO2Y (Y= OR, Ar', Cl) with Alkali Amalgams
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The dependence of the yields of the reductive fission of hexyl benzenesulfonate and mesitylphenyl sulfone with alkali-metal amalgams (primarily lithium amalgam) was studied under standard conditions in toluene using a series of eight aprotic and six protic solvents as cosolvents.Yields about 5percent were measured in toluene, but addition of equimolar amounts (w.r.t. ester or sulfone) of the alcohols methanol, ethanol, isopropyl alcohol or tert-butyl alcohol as co-solvent raised the yields to 80 - 100percent (Fig. 1).In toluene, portion-wise addition of substoichiometric amounts (w.r.t ester) of the cosolvent DMF, THF, dioxane and isopropyl alcohol resulted in the values recorded in Fig. 2.The observed effects are attributed to the different solubilities of Li+-solutions (of unknown composition) in toluene.A reaction mechanism for the reductive fission of ArSO2Y (Y = OR, Ar', Cl) with alkali-metal amalgams is proposed.
- Horner, Leopold,Schmitt, Rolf-Erhard
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p. 469 - 474
(2007/10/02)
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