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CAS No. : | 3112-88-7 | MDL No. : | MFCD00025040 |
Formula : | C13H12O2S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FABCMLOTUSCWOR-UHFFFAOYSA-N |
M.W : | 232.30 | Pubchem ID : | 76561 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.08 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 64.02 |
TPSA : | 42.52 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.26 cm/s |
Log Po/w (iLOGP) : | 1.92 |
Log Po/w (XLOGP3) : | 2.05 |
Log Po/w (WLOGP) : | 3.59 |
Log Po/w (MLOGP) : | 3.07 |
Log Po/w (SILICOS-IT) : | 2.66 |
Consensus Log Po/w : | 2.66 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.93 |
Solubility : | 0.274 mg/ml ; 0.00118 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.57 |
Solubility : | 0.623 mg/ml ; 0.00268 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -5.25 |
Solubility : | 0.0013 mg/ml ; 0.00000561 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.49 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium permanganate; iron(III) chloride In acetonitrile at 23℃; for 1.25h; | |
100% | With dihydrogen peroxide; titanium(IV) oxide In acetonitrile at 20℃; for 10h; | |
99% | With trifluoroacetyl peroxide In trifluoroacetic acid at 30℃; |
99% | With manganese(II) sulfate; dihydrogen peroxide; sodium hydrogencarbonate In water; acetonitrile at 20℃; for 0.25h; | |
99% | With aluminium trichloride; 3-carboxypyridinium chlorochromate In acetonitrile for 0.0166667h; microwave irradiation; | |
99% | With dihydrogen peroxide; tantalum pentaethoxide In methanol at 45℃; for 2.5h; | |
99% | With dihydrogen peroxide; tantalum pentaethoxide In methanol at 45℃; for 2.5h; chemoselective reaction; | |
99% | With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; dihydrogen peroxide at 25℃; for 0.216667h; Neat (no solvent); chemoselective reaction; | |
99% | With dihydrogen peroxide In water; acetonitrile at 20℃; for 3.16667h; Green chemistry; chemoselective reaction; | |
99% | With selenium(IV) oxide; dihydrogen peroxide In water; ethyl acetate chemoselective reaction; | 3.2. Synthesis of Sulfones 2a-g General procedure: In a 2 mL volumetric ask, ethyl acetate was added to suldes 1a±c,e±g (1.0 mmoL) or sulde1d, (0.5 mmoL) to make up the required volume. (Solution A: 0.5 M (1a-c,e-g). In the case of 1d, theconcentration was optimized at 0.25 M) In a 2 mL volumetric flask, 0.1 mmoL of SeO2 (11 mg) andH2O2 30 wt. % (10 mmoL, 1.025 mL) were poured, and then water was added until the desired volumewas reached. (Solution B: 0.05 M (SeO2) and 5 M (H2O2). In the case of 1d, a dierent concentrationwas optimized at 0.025 M (SeO2) and 2.5 M (H2O2)). |
99% | With dihydrogen peroxide In acetonitrile at 25℃; for 0.0833333h; | General procedure for the preparation of sulfones General procedure: To a mixture of sulfide (1 mmol) and AgCeO2 (0.05 g) in2 cm3acetonitrile, 0.3 cm330% H2O2(3 equiv.) was added,and the mixture was stirred at room temperature until thecomplete consumption of sulfide (monitored by TLC). Aftercompletion of the reaction, 10 cm3acetonitrile was addedto the reaction mixture and the mixture heated for 10 minat 50 °C. After that, the catalyst was separated from thereaction mixture by filtration and the organic residue wasextracted with 20 cm3EtOAc, washed with 10 cm3distilledwater, dried over MgSO4,and recrystallized in a mixture ofEtOH and H2Oto obtain the pure product. |
98% | With dihydrogen peroxide; zirconium(IV) chloride In methanol at 20℃; for 0.0333333h; | |
98% | With 30percent aq. H2O2 In methanol at 20℃; for 4h; | |
98% | With dihydrogen peroxide In ethanol at 50℃; for 0.666667h; | |
98% | With dihydrogen peroxide In nitromethane at 20℃; for 2.5h; | |
98% | With dihydrogen peroxide In ethanol at 50℃; for 0.166667h; Green chemistry; | |
97% | With Oxone; aluminium trichloride for 0.5h; Heating; | |
97% | With caro's acid; silica gel In acetonitrile for 5h; Heating; | |
97% | With chromium(VI) oxide; periodic acid In ethyl acetate; acetonitrile at -35℃; for 1.75h; | |
97% | With aluminium trichloride; butyltriphenylphosphonium dichromate In acetonitrile for 0.0416667h; microwave irradiation; | |
97% | With N-methylpyrrolidine-2-one hydrotribromide; dihydrogen peroxide In water; acetonitrile at 80℃; for 0.133333h; | |
97% | With N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium bis(permanganate); acetic acid In acetonitrile at 20℃; for 0.0333333h; | |
97% | With tert.-butylhydroperoxide In water; acetonitrile at 60℃; for 4.5h; Inert atmosphere; | |
97% | With borax; dihydrogen peroxide; sodium hydroxide In methanol; water at 20℃; for 3h; chemoselective reaction; | |
97% | With 1,3,5-trichloro-2,4,6-triazine; dihydrogen peroxide In water; acetonitrile at 20℃; for 0.283333h; chemoselective reaction; | General procedure for the preparation of sulfones General procedure: To a mixture of sulfide (1 mmol) and TCT (1 mmol, 0.184 g) in acetonitrile (5 mL) was added 30% H2O2 (2 mmol, 0.2 mL). The mixture was stirred at room temperature for the appropriate period of time until complete consumption of the starting material as observed by TLC. After completion of the reaction, H2O (10 mL) was added to the reaction mixture which was then extracted with EtOAc (4 × 5 mL) and the combined extracts were dried (MgSO4). The filtrate was evaporated and the corresponding sulfone was obtained as the only product (Table 1). |
97% | With dihydrogen peroxide In methanol at 60℃; for 8h; Green chemistry; | 2.6. General procedure for catalytic oxidation of sulfides to sulfones General procedure: To a stirred solution of 5 mmol sulfide in 5 mL water, 0.01 mmol of Ti containing catalyst [PATi (2.81 mg) or PMATi (3.77 mg)] was added, followed by addition of 50% H2O2 (1.36 mL, 20 mmol) in a round bottom flask. The Ti: substrate molar ratio was maintained at 1 : 500 and the substrate: H2O2 molar ratio at 1 : 4. The reaction was conducted at 80 °C temperature. The reaction was monitored by thin-layer chromatography (TLC) and GC. After completion of the reaction, the system was allowed to cool to room temperature. The sulfone obtained was then isolated, purified and characterized by following similar procedure as mentioned under above section. |
96% | With 3-chloro-benzenecarboperoxoic acid In diethyl ether for 10h; Ambient temperature; | |
96% | With potassium permanganate at 20℃; for 1h; | |
96% | With dihydrogen peroxide In ethanol; water for 2h; Reflux; | |
96% | With niobium carbide; dihydrogen peroxide In ethanol; water at 60℃; for 4h; chemoselective reaction; | |
95% | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane at 25 - 28℃; for 0.75h; | |
95% | With dihydrogen peroxide; urea; trifluoroacetic anhydride In acetonitrile for 1.5h; Ambient temperature; | |
95% | With potassium permanganate In acetonitrile at 20℃; for 55h; | |
95% | With 1H-imidazole; manganese(II) tetraphenylporphyrinate; tetra-n-butylammonium hydrogen monopersulfate In dichloromethane at 20℃; for 0.0166667h; | |
95% | With dihydrogen peroxide; titanium tetrachloride In acetonitrile at 25℃; for 0.0333333h; | |
95% | With aminosulfonic acid; dihydrogen peroxide In neat (no solvent) at 20℃; for 0.916667h; Green chemistry; chemoselective reaction; | |
95% | With tetra-n-butylammonium peroxomonosulfate In water at 25℃; for 0.75h; chemoselective reaction; | |
95% | With tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 0.333333h; | |
94% | With silica gel; magnesium monoperoxyphthalate hexahydrate In dichloromethane for 1.25h; Heating; | |
94% | With formic acid; dihydrogen peroxide; urea for 2h; Ambient temperature; | |
94% | With dihydrogen peroxide In 1,2-dichloro-ethane for 0.3h; Reflux; | |
94% | With dihydrogen peroxide In methanol at 40℃; for 0.416667h; chemoselective reaction; | |
94% | With dihydrogen peroxide In water at 20℃; for 10h; | |
94% | With dihydrogen peroxide In ethanol; water at 50℃; for 0.166667h; Green chemistry; chemoselective reaction; | |
94% | With dihydrogen peroxide; C16H16N3O5V In ethanol; water for 0.333333h; Reflux; | 2.5 Generalized method for the selective oxidation of sulfides to sulfones catalyzed by [VO2(HL)] General procedure: A solution of methylphenyl sulfide (1mmol), 30% aqueous H2O2 (4mmol) and [VO2(HL)] complex (1mol%) in 5mL of EtOH, was refluxed with vigorous stirring. The catalytic conversion is continuously observed by employing thin layer chromatography by using a 70:30 mixture of n-hexane and diethyl ether as eluent. After that, the reaction mixture was cooled to room temperature and then the hot ethanol (3mL) was added up and the contents were stirred for 10min. At this stage, the catalyst is recovered by filtration and washed thrice with hot ethanol. From the filtrate the solvent was evaporated slowly to get the desired refined products. The products gained after the completion of the catalytic cycle were characterized spectroscopically and then the data was compared with the standard samples. |
93% | With dihydrogen peroxide In acetonitrile at 20℃; for 0.5h; | |
93% | With tert.-butylhydroperoxide; lanthanum(III) oxide In water; ethyl acetate at 150℃; for 5h; | |
92% | With L-alanin; silica gel; Chloro-hydroxy-dioxo-chromium In tetrachloromethane at 65℃; for 5h; | |
92% | With dihydrogen peroxide In acetonitrile at 20℃; for 1h; chemoselective reaction; | 2.4. Synthesis of sulfoxides and sulfones General procedure: To a stirred suspension of the selected sulfide (1 mmol) and the heterogeneous catalyst PW12(at)Al-MCF (3 mol%) in methanol (5 ml), H2O2 (8 mmol) was added in one portion. The slurry was stirred at room temperature for 20 min. The catalyst was filtered off and washed with methanol (5 ml). Ethyl acetate (5 ml) was added and resulting solution was dried with anhydrous sodium sulfate and evaporated in vacuo to afford the crude product which was purified by column chromatography on silica gel (10% EtOAc in hexane) to afford the pure sulfoxide. |
92% | With dihydrogen peroxide In water; acetonitrile at 50℃; for 3h; chemoselective reaction; | General procedure for the oxidation of sulfide to sulfone General procedure: A solution of sulfide (1 mmol) and catalyst (100 mg), in acetonitrile (9 mL), was added to H2O2 35% (w/v) (10 mmol). The mixture was stirred at 50 °C for a time period (see Tables 1 and 2). The solvent was evaporated and then H2O (5 mL) was added. The substrate was extracted with toluene (2 × mL) and dried with anhydrous Na2SO4; filtration and evaporation afforded the corresponding sulfoxides. The crude solids were purified by recrystallization to affordthe pure sulfones |
92% | With dihydrogen peroxide In water at 20℃; for 0.5h; chemoselective reaction; | General procedure for the oxidation of sulfides to sulfones General procedure: To a mixture of sulfide (1 mmol) and catalyst (0.04 g), H2O2 30%(v/v) (0.28 g, 2.5 equiv.) was added and stirred at room temperature for a specified time. After completion of the reaction, as indicated on thin-layer chromatography (TLC), ethyl acetate (20 mL) was added and the mixture was centrifuged to separate the catalyst. The filtrate was washed with brine and dried over anhydrous Na2SO4. Purification of the combined organics by preparative TLC (hexane-ethyl acetate, 10:1) provided pure products. The recycled catalyst was washed with ethyl acetate and acetone. After being dried at 60 °C, it can be reused without further purification. All of the products were known and identified by comparison of their melting points and spectral data with those reported in the literature 2.4. |
92% | With water; N-fluorobis(benzenesulfon)imide at 20℃; for 24h; chemoselective reaction; | |
91% | With dihydrogen peroxide In acetic acid | |
91% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 4-methoxyisoquinoline; oxygen; copper(II) sulfate In methanol at 65℃; for 48h; Schlenk technique; Sealed tube; Green chemistry; | 12 Example 12: Preparation of phenyl p-toluenesulfonic acid from phenyl p-toluene sulfide TEMPO (3.9 mg, 0.025 mmol) was added to a 100 mL Schlenk reaction tube in turn. Methanol (1mL), CuSO4 (4.0mg, 0.025mmol), 4-methoxyisoquinoline (39.8 mg, 0.25 mmol), Phenyl p-toluene sulfide (100.2 mg, 0.5 mmol), Filled with 1 atm of oxygen, The sealed reaction tube was heated to 65 ° C for 48 h. After the reaction is completed, it is cooled to room temperature. Add the right amount of ethyl acetate, A blue solid precipitated in the reaction solution. Filtration, the filtrate is concentrated under reduced pressure, and purified by column chromatography to obtain The product has a yield of 91%. |
90% | With dihydrogen peroxide; boric acid at 20℃; for 0.5h; neat (no solvent); chemoselective reaction; | |
90% | With dihydrogen peroxide In water at 20℃; for 0.583333h; | |
90% | With O40PW12(3-)*3C14H16NO3S(1+); dihydrogen peroxide In ethanol; water at 60℃; for 1h; Green chemistry; | Oxidation of solid sulfur compounds General procedure: To a stirred suspension of the substrate (5 mmol), catalyst (0.2 g, 1.0 mol%) in H2O: EtOH (7:3v/v, 10 mL), 30% aq. H2O2 (1.1 mL, 10 mmol) was added in one portion. The slurry was stirred at 60 °C for 45 min. The reaction mixture was cooled to 10 °C, and the catalyst was separated by filtration. The corresponding sulfoxide product was extracted with Et2O from the reaction mixture. Evaporation of the solvent afforded the crude product. The crude product was purified by column chromatography on silica gel using EtOAc/hexane as eluent (method (c)). Similar method was utilized to produce sulfones. In this case 3.4 mL of 30% aq. H2O2 (30 mmol) was used for 60 min (method (d)). |
90% | With tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 3h; | |
90% | With 2,2,2-Trifluoroacetophenone; dihydrogen peroxide; acetonitrile In <i>tert</i>-butyl alcohol at 20℃; for 1h; Green chemistry; | Organocatalytic Oxidation of Sulfides to Sulfones; General Procedure General procedure: Sulfide (1.00 mmol) was placed in a round-bottom flask, followed by t-BuOH (0.5 mL), 2,2,2-trifluoroacetophenone (34.8 mg, 0.20 mmol), aq buffer solution (0.5 mL, 0.6 M K2CO3/4 × 10-4 M EDTA disodium salt), MeCN (0.15 mL, 3.00 mmol) and 30% aq H2O2 (0.36 mL, 3.00 mmol). The reaction mixture was stirred for 1-5 h. The reaction was quenched with 1 M HCl (5 mL) and extracted with CHCl3 (3 × 10 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to afford the desired product. |
90% | With dihydrogen peroxide at 20℃; for 0.166667h; Green chemistry; chemoselective reaction; | |
90% | With oxygen; epi-Cercosporin In methanol at 25℃; for 24h; Irradiation; | 1 Example 1 Catalytic Synthesis of Benzyl Phenyl Sulfone by Cercosporin Catalyst In a 10 mL reaction tube, cercosporin (0.005 mmol) and benzyl phenyl sulfide (0.5 mmol) were sequentially added.2mL of methanol, then oxygen protection, 15W white light irradiation, room temperature 25 ° C reaction for 24h.The reaction solution was evaporated to dryness by rotary evaporation, and then evaporated, and then evaporated, eluent, eluent, ethyl acetate/ petroleum ether (v: v = 1:5).The benzyl phenyl sulfone was obtained in a yield of 90%. |
89% | With 1,3,5-trichloro-2,4,6-triazine; dihydrogen peroxide In tetrahydrofuran at 20℃; for 0.416667h; | |
88% | With HOF* CH3CN; water In dichloromethane at -20℃; for 0.0833333h; | |
88% | With copper phthalocyanine; tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 1h; chemoselective reaction; | |
87% | With sodium periodate; silica gel In dichloromethane for 0.0416667h; Irradiation; | |
87% | With potassium permanganate; Rexyn 101 H ion exchange resin In dichloromethane for 5.3h; Heating; | |
87% | With sodium hypochlorite; silica gel In dichloromethane; water for 0.15h; Microwave irradiation; chemoselective reaction; | |
87% | With sodium bromate In water at 80℃; for 0.5h; Ionic liquid; | Oxidation of sulfides, tellurides and phosphines; general procedure General procedure: A mixture of sodium bromate (3.12 mmol), and substrate 1 or 3 or 5(1.04 mmol) in 4 mL of [bmim]HSO4:H2O (3:1, v/v) was placed in a 50 mL round-bottomed flask mounted over a magnetic stirrerand fitted with an air condenser. The contents were heated in an oil-bath maintained at 80 °C for the time specified in Table 2 and 3.The progress of the reaction was monitored by TLC using ethylacetate:petroleum ether (50:50, v/v) as eluent. After completion ofthe reaction, the contents were allowed to cool to room temperature.A saturated solution of sodium thiosulfate (~5 mL) was added into thereaction mixture in order to remove excess unreacted bromine. Themixture was poured into a beaker containing ice cold water (~30 mL)and stirred well. The solid product was filtered under suction pumpand recrystallised. The products were characterised by its m.p., IR andNMR spectra. |
87% | With palladium; dihydrogen peroxide In methanol at 100℃; for 6h; Green chemistry; chemoselective reaction; | |
87% | With urea hydrogen peroxide adduct In ethanol at 20℃; for 0.5h; | 2.1. General procedure for catalytic oxidation of organic sulfides to sulfones Organic sulfide (1.0 mmol), UHP (5.0 mmol) and catalyst (0.05 mmol) were stirred in ethanol (5 mL) at room temperature and the progress of the reaction was monitored using thin layer chromatography (TLC). After completion of the reaction, precipitate formed was filtered off, washed with cold ethanol and dried to obtain the pure organic sulfone. In case of soluble organic sulfones, solvent was evaporated under reduced pressure; residue was triturated with dichloromethane (5 mL) and filtered to remove the insoluble urea and catalyst. The filtrate containing sulfone was dried and recrystallized from dichloromethane/hexane mixture. |
86% | With manganese(IV) oxide; potassium permanganate at 20℃; for 1.41667h; ultrasonic irradiation; | |
86% | With 3-oxo-1λ3-benzo[d][1,2]iodaoxol-1(3H)-yl 2,2,2-trifluoroacetate In acetonitrile for 16h; Reflux; | Procedure for the synthesis of sulfones 10a-h General procedure: The mixture of sulfide (0.5 mmol) and reagent 8 (413 mg, 2.4 equiv) in acetonitrile (3 mL) was heated atreflux temperature for 16-20 h. The course of reaction was monitored by TLC. After completion ofreaction, saturated solution of sodium bicarbonate (5 mL) was added to the reaction mixture andextracted with ethyl acetate (3 X 15 mL). The combined organic layer was dried over anhydrous sodiumsulphate and concentrated under vacuum. The crude products were purified by column chromatographyon silica gel using EtOAc-hexane (1:3) and isolated products were characterized as sulfones 10 byspectroscopic analysis. |
85% | With potassium permanganate; copper(II) sulfate at 20℃; for 12h; | |
82% | With potassium permanganate; N-benzyl-N,N,N-triethylammonium chloride; benzoic acid In dichloromethane; water for 3h; | |
82% | With 3-butyl-1-methyl-1H-imidazolium perrhenate; dihydrogen peroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate In water at 60℃; for 5.5h; Schlenk technique; Inert atmosphere; Green chemistry; | 2.3 Catalytic oxidation of sulfides General procedure: To a stirred solution of sulfide (10mmol) and [C4mim][ReO4] (0.1955g, 5 mol%) in [C4mim][BF4] (2mL), an aqueous solution of hydrogen peroxide (35% in water) (3.5mL, 40mmol) is added in 2-3 portions at 60°C. The progress of the reaction is followed by TLC. The reaction mixture is extracted with diethyl ether (5×10mL) and the extract is dried over anhydrous MgSO4. The yield and selectivity of methyl phenyl sulfone are calculated from calibration curves (r2>0.999) recorded using 3-methylanisole and 1,4-diacetylbenzene as internal standard. The crude product is obtained by rolling evaporation and purified by column chromatography separation (silica gel using hexane/ethyl acetate 90:10 v/v). The RTIL phase is diluted with CH2Cl2 and then treated with MnO2 to destroy the excess peroxide. The obtained liquid is first dried over anhydrous MgSO4 and then for 4h in vacuo at 50°C to remove CH2Cl2. Fresh substrate and hydrogen peroxide are then added for a new reaction cycle. All products are characterized by melting point, 1H NMR, 13C NMR and IR spectroscopy (see Supporting information). |
82% | With urea-2,2-dihydroperoxypropane In tetrahydrofuran at 20℃; for 1.16667h; Green chemistry; chemoselective reaction; | Typical Procedure for Selective Oxidation of Methyl(phenyl)sulfide Sulfides to (methylsulfinyl)benzene and(methylsulfonyl)benzene General procedure: To a stirred solution of sulfide (1 mmol, 0.124 g) and THF (4 mL), urea-2,2-dihdroperoxypropane (2 or 6 mmol, 0.336-1.00 g pending to products) was added and the mixture was stirred at room temperature for an appropriate time. After completion of the reaction as monitored by TLC, saturated aqueous solution of Na2SO3 (2 mL of 1 M solution) was added to quench the excessive oxidant remaining in the mixture. Then water (10 mL) was added to the mixture and extracted using chloroform (3 × 5 mL) and dried over anhydrous MgSO4. After evaporation of solvent under reduced pressure, chromatography on silica gel was used to give pure products. |
81% | With N,N'-bis(salicylidene)-1,2-phenylene diaminocobalt(II); oxygen; isobutyraldehyde In acetonitrile at 70℃; for 6h; | |
81% | With phenanthroline hydrotribromide; dihydrogen peroxide In water; acetonitrile at 20℃; for 0.583333h; | Oxidation of benzyl phenyl sulfide General procedure: 30% hydrogen peroxide, 1.5 mL (10 mmol) was added drop wise to a stirred solution ofbenzyl phenyl sulfide, 2 g (10 mmol) and PhenHTB, 0.042 g (10 mol %) in acetonitrile-water mixture (10 mL, 1:1) at roomtemperature for an appropriate time. After completion of the reaction as monitored by TLC, the reaction mixture was poured inwater and the excess hydrogen peroxide was destroyed by the addition of aq. sodium bisulfite followed by the filtration through asmall Buckner funnel. After filtration the organic products were extracted with ether. The ether layer was washed with water (2mL) and dried over Na2SO4. The organic solvent was removed under reduced pressure to give the corresponding sulfoxide. Theproducts were further purified by column chromatography on silica gel using ethyl acetate/hexane (1:4) as eluent. Evaporation ofthe solvent yielded the corresponding benzyl phenyl sulfoxide (10, Table 1). The reaction time and yield of the products arepresented in the Table 1. |
81% | With 1,2-diphenyl-1,1,2,2-tetrahydroperoxyethane In tetrahydrofuran at 20℃; for 1.1h; Green chemistry; chemoselective reaction; | General procedures for selective oxidation of sulfdes tosulfoxides or sulfones General procedure: To a stirred solution of sulfde (1 mmol) and THF (4 mL),THPDPE (1 up to 5.5 mmol (0.310 up to 1.70 g) dependingon the substrates and products) was added and the mixture wasstirred at room temperature for an appropriate time. After completion of the reaction, as monitored by TLC, a saturated aqueous solution of Na2SO3 (2 mL of 1 M solution) was added toquench the excessive oxidant that was remained in the mixture.Water (10 mL) was added to the mixture and extracted usingchloroform (3 × 5 mL) and dried over anhydrous MgSO4. Afterevaporation of solvent under reduced pressure chromatographyon silica gel was used to give pure products. |
81% | With dihydrogen peroxide In water at 75℃; for 4h; | |
78% | With potassium permanganate supported on montmorillonite K10 at 20℃; for 2h; | |
78% | With oxygen at 100℃; for 20h; Schlenk technique; chemoselective reaction; | |
70% | With tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 1h; chemoselective reaction; | |
8.2% | With dihydrogen peroxide; calcium(II) trifluoromethanesulfonate In acetonitrile at 29.84℃; for 6h; | |
8% | With dihydrogen peroxide In ethanol; n-heptane; water at 60℃; for 1h; | Oxidation of solid sulfides General procedure: Solid sulfides were oxidized to the corresponding sulfonesby stirring a solution of the sulfide (1 mmol) and the catalyst(0.15 g) in n-heptane-ethanol (v/v, 4:2). Then a certain amountof H2O2 (30% aq.) was added as the oxidant. The mixture wasstirred for a specified time at 60 °C, and the reaction was monitoredusing thin-layer chromatography. After completion ofthe reaction, the catalyst was separated from the reaction solutionusing an external magnet. The corresponding sulfoneproducts were separated from the reaction mixture. The solventwas evaporated to generate the crude product. The crude product was purified by column chromatography on silica gelusing hexane/ethyl acetate as the eluent (method b). |
With oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 1.25h; various reaction conditions; | ||
With dihydrogen peroxide; acetic acid | ||
With 3-chloro-benzenecarboperoxoic acid | ||
With chromium(VI) oxide In acetic acid at 90 - 100℃; for 0.5h; | ||
With phthalic anhydride; urea In acetonitrile for 1.5h; Ambient temperature; | ||
With dihydrogen peroxide In acetic acid | ||
With tetrabutylammonium polychromiumphosphotungstate trihydrate; dihydrogen peroxide In water; acetonitrile at 25℃; for 0.166667h; Green chemistry; chemoselective reaction; | Typical procedure for the catalytic oxidation of sulfides to sulfones General procedure: PWCr catalyst (0.0245 mmol), CH3CN (3 mL), sulfide (1 mmol), and hydrogenperoxide (4 mmol, 30% aq solution) were added to a glass tube as the reaction vessel. The reaction was carried out at 298 K. The mixture was sampled periodically and analyzed by GC. After completion of the reaction, the product was extracted with CH2Cl2 and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to give the corresponding pure sulfone. The products were identified by comparison of their 1H NMR and 13C NMR signals with the literature data (see Supplementary Data, Figures S5-S18). | |
80 %Chromat. | With potassium permanganate In o-xylene at 20℃; for 11h; Green chemistry; | |
With 4C16H36N(1+)*PW11CrO39(4-)*3H2O; dihydrogen peroxide In water at 25℃; for 0.5h; Green chemistry; | General procedure for the oxidation of sulfides to sulfones: The sulfide (1mmol) was added to a solution of 30% H2O2 (6.5 equiv) and TBAPWCr (16.5μmol), and the mixture was stirred at room temperature for the time specified in Table2. The progress of reactions was monitored by TLC and GC. After completion of the reaction, the product was extracted with ethyl acetate. Further purification was achieved by short-column chromatography on silica gel with EtOAc/n-hexane (1/10) as eluent. All of the products were known and characterized by 1HNMR and 13CNMR (see Supplementary data, Figs. S3-S15) [38-41]. | |
With oxygen; isobutyraldehyde In acetonitrile at 20℃; for 1.5h; Green chemistry; | ||
With dihydrogen peroxide In acetonitrile at 25℃; for 0.5h; Reflux; | ||
With (n-Bu4N)6(Mo7O24); dihydrogen peroxide In acetonitrile at 22℃; for 1h; | ||
With dihydrogen peroxide In acetonitrile at 20℃; for 0.5h; | ||
With oxygen; LmbC oxygenase; glycerol; NADPH; flavin adenine dinucleotide; sodium chloride In 1,4-dioxane at 24℃; for 24h; Enzymatic reaction; | ||
With dihydrogen peroxide; C17H19MoN3O7 In ethanol; water Reflux; Green chemistry; | 2.3. Generalized method for the catalytic selective oxidation of sulfides by MoO 2 L(CH 3 OH) complex General procedure: A solution of methylphenyl sulfide (1 mmol), 30% aqueous H 2 O 2 (4 mmol), MoO 2 L(CH 3 OH) complex (1 mol%) and chlorobenzene (1 mmol) as internal standard in 5 mL of EtOH, was refluxed with vigorous stirring. The catalytic conversion is continuously observed by employing thin layer chromatography by using a 70:30 mixture of n -hexane and diethyl ether as eluent. After that, the reaction mixture was cooled to room temperature and then the hot ethanol (3 mL) was added up and the contents were stirred for 10 minutes. On complete conversion, the resultant mixture was filtered offand then the solvent was evaporated slowly to get the desired refined products. The products gained after the completion of the catalytic cycle were characterized spectroscopically and then the data was compared with the standard samples. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With aluminum oxide for 2h; Irradiation; | |
96% | With 1-butyl-3-methylimidazolium Tetrafluoroborate In water at 60℃; for 2h; | |
96% | In N,N-dimethyl-formamide at 80℃; for 12h; |
85% | In water at 120℃; for 0.5h; microwave irradiation; | |
51% | With C11H20O4*2C18H37NO5; copper(I) bromide In water at 100℃; for 12h; | |
With ethanol | ||
In ethanol | ||
In N,N-dimethyl-formamide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(i) MeLi, HMPT, THF, (ii) /BRN= 102527/, (iii) MeMgI; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.166667h; Stage #2: benzyl chloride In tetrahydrofuran; hexane at -78 - 20℃; | |
(i) LiNEt2, HMPT, benzene, Et2O, (ii) /BRN= 471308/; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methyllithium In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide 1.) -70 deg C, 5 min; 2.) RT; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; | |
With n-butyllithium In tetrahydrofuran; hexane for 0.5h; Ambient temperature; | ||
With n-butyllithium 1.) THF, hexane, -78 deg C, 30 min, 2.) THF, hexane, -78 deg C -> room temperature, 1 h; Multistep reaction; |
Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78 - 20℃; for 1h; | ||
Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78℃; for 1h; | ||
Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; methanol; hexane at -74℃; for 0.5h; Inert atmosphere; Automated synthesizer; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane; deuteromethanol at 15℃; for 1h; Inert atmosphere; Automated synthesizer; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With lithium diisopropyl amide In tetrahydrofuran 1.) 0 deg C, 1h, 2.) reflux, 15 h; | |
With lithium diisopropyl amide In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With hexachloroethane; sodium hydroxide In dichloromethane; water at 25℃; | |
95% | With tetrachloromethane; potassium hydroxide In <i>tert</i>-butyl alcohol at 25℃; | |
80% | With tetrachloromethane; sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane for 24h; |
With potassium hydroxide In tetrachloromethane; water | 3 EXAMPLE 3 EXAMPLE 3 1.16 g. phenyl benzyl sulfone and 5.6 g. of powdered potassium hydroxide were stirred in 10 ml. of carbon tetrachloride and 10 ml. of tertiary butyl alcohol under reflux for 30 minutes. Excess solvent was removed under vacuum, a small proportion of water was added to the residue, and the residue was extracted with ether. The ether extract was washed with water, dried with anhydrous magnesium sulfate, filtered and concentrated under a vacuum, yielding 1.5 g. of α,α-dichlorobenzyl phenyl sulfone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | at 60℃; for 24h; | |
95% | With tetra-(n-butyl)ammonium iodide; potassium iodide In N,N-dimethyl-formamide at 20℃; for 12h; | |
95% | With 1-butyl-3-methylimidazolium Tetrafluoroborate In water at 60℃; for 1h; |
95% | In N,N-dimethyl-formamide at 80℃; for 4h; | |
93% | In N,N-dimethyl-formamide at 80℃; for 4h; Inert atmosphere; | |
93% | With ceramic boron carbonitride In dimethyl sulfoxide at 25℃; for 72h; Schlenk technique; Inert atmosphere; Irradiation; | |
90% | In tetrahydrofuran; N,N-dimethyl-formamide at 80℃; | |
76% | With tetra-(n-butyl)ammonium iodide In acetonitrile Reflux; Inert atmosphere; | |
72% | With potassium iodide In N,N-dimethyl-formamide at 20℃; for 16h; | |
53% | With C11H20O4*2C18H37NO5; copper(I) bromide In water at 100℃; for 12h; | |
In N,N-dimethyl-formamide | ||
With tetra-(n-butyl)ammonium iodide In tetrahydrofuran at 50℃; for 4h; | ||
With triethylamine In tetrahydrofuran; N,N-dimethyl-formamide | ||
With tetra-(n-butyl)ammonium iodide; potassium iodide In dimethyl sulfoxide at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With ammonium chloride; zinc In tetrahydrofuran; water at 0℃; for 3h; | |
80% | With indium In water at 0℃; for 4h; | |
75% | With samarium; mercury dichloride In tetrahydrofuran at 50℃; for 2.5h; |
74% | With samarium; nickel dichloride In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; | |
72% | With nickel In N,N-dimethyl-formamide at 60℃; for 1.5h; | |
With sodium O,O-diethylphosphotellurite; N-benzyl-N,N,N-triethylammonium chloride 1.) EtOH, THF, 20 min, 2.) reflux, 4 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: benzenesulfonyl chloride With magnesium In tetrahydrofuran at 25℃; for 1h; Inert atmosphere; Schlenk technique; Sonication; Stage #2: benzyl chloride With sodium iodide In tetrahydrofuran; dimethyl sulfoxide at 60℃; for 1h; Inert atmosphere; Schlenk technique; Sonication; | |
80% | In water at 20℃; for 4.5h; | |
With sodium O,O-diethylphosphotellurite; N-benzyl-N,N,N-triethylammonium chloride 1.) EtOH, THF, 20 min, 2.) reflux, 4 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With naphthalene; lithium In tetrahydrofuran at -78 - 20℃; for 5h; | |
46% | With naphthalene; lithium In tetrahydrofuran at -78 - 20℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: Benzyl phenyl sulfone With sodium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; | |
33% | Stage #1: Benzyl phenyl sulfone In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; | |
With n-butyllithium 1.) THF; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; dihydrogen peroxide at 25℃; for 0.166667h; Neat (no solvent); chemoselective reaction; | |
95% | With tert.-butylhydroperoxide; silica gel In dichloromethane at 25℃; for 6h; | |
95% | With tert.-butylhydroperoxide; silica gel In dichloromethane at 25℃; for 6h; |
91% | With sodium hypochlorite In acetonitrile for 1h; Ambient temperature; | |
100 % Chromat. | With 1H-imidazole; manganese(II) tetraphenylporphyrinate; tetra-n-butylammonium hydrogen monopersulfate In dichloromethane at 20℃; for 0.0166667h; | |
With nitric acid In acetonitrile at 20℃; for 80h; | ||
Multi-step reaction with 2 steps 1: 1,3,5-trichloro-2,4,6-triazine; potassium iodide / acetonitrile / 0.17 h / 20 °C 2: 1,3,5-trichloro-2,4,6-triazine; dihydrogen peroxide / water; acetonitrile / 0.28 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.6% | With C64H64N4O6Ti2; dihydrogen peroxide In dichloromethane; water at -20℃; for 48h; optical yield given as %ee; enantioselective reaction; | |
1: 69.4% 2: 12.6% | With C68H72N4O6Ti2; dihydrogen peroxide In dichloromethane; water at 0℃; for 16h; optical yield given as %ee; enantioselective reaction; | |
22% | With (R,R)-[iron(III)chloride(C6H10(NCHC6H2(tBu)2O)2)]; iodosylbenzene In dichloromethane at 20℃; for 15h; optical yield given as %ee; enantioselective reaction; |
15% | With iodosylbenzene In dichloromethane at 20℃; for 5h; | |
1: 53 % ee 2: 11% | Stage #1: Benzyl phenyl sulfide With 2C2H7N*3Cd(2+)*3C14H8O4(2-)*19H2O*2H(1+)*C114H132N12O12Ti4(2-) In dichloromethane at 20℃; for 0.333333h; Stage #2: With dihydrogen peroxide In dichloromethane; water for 72h; | |
With titanium(IV) isopropylate; Cumene hydroperoxide; (+)-(2R,2'R,2''R)-triphenylethan-2-olamine In 1,2-dichloro-ethane at 0℃; Yield given. Yields of byproduct given; | ||
With titanium(IV) isopropylate; Cumene hydroperoxide; (+)-(2R,2'R,2''R)-triphenylethan-2-olamine In 1,2-dichloro-ethane at 0℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With (S)-(-)-2-(N-3,5-diiodosalicylidene)amino-3,3-dimethyl-1-butanol; dihydrogen peroxide; 4-methoxybenzoic acid In dichloromethane at 20℃; for 16h; Title compound not separated from byproducts; | ||
With (S)-(-)-2-(N-3,5-diiodosalicylidene)amino-3,3-dimethyl-1-butanol; dihydrogen peroxide In dichloromethane at 20℃; for 0.5h; Title compound not separated from byproducts; | ||
With titanium(IV) isopropylate; tert.-butylhydroperoxide; (4S,5R)-4,5-dihydro-4,5-diphenyl-2-(2'-hydroxy-3'-tert-butylphenyl)-oxazoline In tetrachloromethane; dichloromethane at 0℃; for 24h; | ||
With Cumene hydroperoxide In 1,2-dichloro-ethane at 0℃; for 6h; Title compound not separated from byproducts; | ||
With Cumene hydroperoxide; (R,R,R)-titanatrane In 1,2-dichloro-ethane at 0℃; for 4h; Title compound not separated from byproducts; | ||
With (S)-C13H17I2NO2; vanadyl acetylacetonate; dihydrogen peroxide In dichloromethane; water at 20℃; for 16h; Title compound not separated from byproducts; | ||
With iodosylbenzene In acetonitrile at 0℃; for 2h; Title compound not separated from byproducts.; | ||
With iodosylmesitylene In acetonitrile at 20℃; for 2h; Title compound not separated from byproducts.; | ||
47.6 %Spectr. | With di-μ-oxo-titanium-(N,N-bis(salicylidene)-ethylenediamine(cyclohexane); dihydrogen peroxide In dichloromethane; water at 25℃; for 3h; optical yield given as %ee; enantioselective reaction; | |
19.0 %Spectr. | With C64H64N4O6Ti2; dihydrogen peroxide In dichloromethane; water at 25℃; for 2h; optical yield given as %ee; enantioselective reaction; | |
With Cumene hydroperoxide; C47H68F3NO6STi In toluene at -30℃; for 36h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With Cumene hydroperoxide; C49H75NO4Ti In dichloromethane at -78℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With bis(acetylacetonate)oxovanadium; 2-[(1S,2S,3R,5S)-3-hydroxymethyl-2,6,6-trimethylbicyclo[3.1.1]hept-2-ylimino]methyl}phenol; dihydrogen peroxide In dichloromethane; water at 20℃; for 3h; optical yield given as %ee; enantioselective reaction; | ||
With titanium(IV) isopropylate; tert.-butylhydroperoxide; 2-benzyl-1,3-diphenylpropane-1,3-diol In toluene at -20℃; for 36h; Molecular sieve; optical yield given as %ee; enantioselective reaction; | Typical experimental procedure for the synthesis of chiral sulfoxides General procedure: To a solution 1,3-diol (16 mg, 0.05 mmol) containing MS4Å (70 mg) was added Ti(O-iPr)4 (7.4 μL, 0.025 mmol) in toluene (1 mL). The mixture was stirred for 2 h at rt and then methyl(p-tolyl)sulfane (68 μL, 0.5 mmol) was added. The mixture was cooled to -20 °C and t-butylhydroperoxide (0.16 mL, 0.8 mmol)18 was added. After stirring for 36 h at the same temperature, the reaction was quenched with 10% aqueous solution of sodium sulfite. The aqueous layer was extracted with ethyl acetate (3 × 15 mL) and organic layer was dried (Na2SO4). The solvent was evaporated under reduced pressure to leave the crude product, which was separated by preparative TLC (3:2; hexane/ethyl acetate) to give 8g (46 mg, 60%). The product was characterised by spectroscopic analysis and the analyses were consistent with the literature. Enantiomeric excess was determined by chiral HPLC on a Chiralcel OD-H (250 × 4.6 mm) column eluting with a hexane/isopropanol (9:1) mixture (1 mL/min, λ = 250 nm). | |
7 % ee | With 1H-imidazole; C84H72ClMnN4O12S4(4-)*4Na(1+); dihydrogen peroxide In methanol; aq. phosphate buffer at 25℃; for 2h; Inert atmosphere; Overall yield = 57 %Chromat.; | 2.3. General procedure for asymmetric sulfoxidation General procedure: Methyl phenyl sulfoxide. Manganese porphyrin complex 1 (1.6 mg, 1 μmol) and imidazole (1.7 mg, 25 μmol) were placed in a test tube under argon. The solvent (375 μL MeOH + 125 μL PBS, pH 7) was then added via syringe, followed by the sulfide (5 μL, 42.3 μmol). Finally, hydrogen peroxide (1.8 μL, 21.2 μmol) was added in one portion to the solution. The reaction was followed by gas chromatography (GC). From GC we knew that the reaction was over after 2 h with a 100% yield containing 1% sulfone. The solution was extracted with dichloromethane three times and then dried over MgSO4. The ee was then determined by HPLC to be 33%. |
55 % ee | With C42H52N4O6Ti2; dihydrogen peroxide In dichloromethane; water at -10℃; for 16h; enantioselective reaction; | |
83 % ee | With C40H46Cl2N4O6Ti2; dihydrogen peroxide In dichloromethane; water at -10℃; for 40h; enantioselective reaction; | |
51 % ee | Stage #1: Benzyl phenyl sulfide With 2C2H7N*3Cd(2+)*3C14H8O4(2-)*19H2O*2H(1+)*C114H132N12O12Ti4(2-) In dichloromethane at 20℃; for 0.333333h; Stage #2: With dihydrogen peroxide In dichloromethane; water for 72h; | |
48 % ee | With 3Cd(2+)*HO(1-)*Br(1-)*2O(2-)*4Ti(4+)*4CH3O(1-)*3C3H7NO*H2O*4C34H42N3O4(3-); dihydrogen peroxide In acetone at 0 - 25℃; for 16.3333h; enantioselective reaction; | |
51 % ee | With dihydrogen peroxide In chloroform at 0℃; for 12h; enantioselective reaction; | |
With C29H44FeN2O5; dihydrogen peroxide; 4-methoxybenzoic acid In dichloromethane; water at 15℃; for 12h; Optical yield = 75 %ee; enantioselective reaction; | ||
79 % ee | Stage #1: Benzyl phenyl sulfide With titanium(IV) isopropylate; C51H54N2O4 In methanol; dichloromethane; water at 20℃; for 0.333333h; Inert atmosphere; Stage #2: With dihydrogen peroxide In methanol; dichloromethane; water at 0℃; for 1.5h; Inert atmosphere; enantioselective reaction; | |
1: 38% ee 2: 21 %Chromat. | With (S,S)-1-(1-carboxy-2-methylpropyl)-3-(1-carboxylate-2-methylpropyl)imidazolium; (x)H2O*MoO(4+)*2O2(2-); dihydrogen peroxide; tetraphenylphosphonium bromide In chloroform; water at 0℃; for 1h; | |
84 % ee | With dihydrogen peroxide; 6,6′-bis[(S)-4-isopropyloxazolin-2-y1]-2,2′-bipyridine; iron(II) chloride In tetrahydrofuran; water at -25℃; for 1h; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With bis(acetylacetonate)nickel(II); n-butyllithium In tetrahydrofuran; hexane at 25℃; for 168h; | |
With bis(acetylacetonate)nickel(II); n-butyllithium 1.) THF, hexane, 25 deg C, 2.) THF, 25 deg C, 7 d; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 95% 2: 1 % Spectr. | With chloro-trimethyl-silane In acetonitrile at -15℃; for 10h; | |
1: 94% 2: 3% | With dihydrogen peroxide In methanol at 0℃; for 1h; | |
1: 90% 2: 5% | With Oxone In water at 25℃; for 4h; Green chemistry; |
1: 90% 2: 5% | With dihydrogen peroxide In ethanol; hexane; water at 80℃; for 1h; | 2.5.3. Oxidation of solid sulfur compounds to sulfones General procedure: A mixture of 0.03 g of the catalyst and 30% H2O2 (10 mmol)aq. was added to a solution of the sulfide (1 mmol) in a mixedsolvent of EtOH and hexane (1:1; 2 mL), and the resulting mixture was stirred at 80 °C. The reaction mixture was cooled toroom temperature and the catalyst was separated using anexternal magnetic field. The corresponding sulfones were extractedwith EtOH from the reaction mixture (Method c, Table2, entries 8-11). |
1: 90% 2: 10% | With dihydrogen peroxide; C14H11ClN3O4V In ethanol; water for 0.25h; Reflux; | 4.5. Catalysis experiments General procedure: In a typical experiment, to a 1 millimolar solution of diphenyl sulfide and VOL (0.004 mmol) or MoO2L (0.006 mmol) in EtOH (10 mL), 30% aqueous H2O2 (2 mmol) was mixed with the reacting stuff and refluxed along with vigorous stirring for a definite period of time and the results are given in Table 1. The monitoring of the catalytic cycle was ensured by TLC (eluent, n-hexane:ethyl acetate, 5:2) while the percentage yield was determined with the help of gas chromatography. The products were then purified with the help of liquid chromatography by using silica gel as a stationary phase and a mixture of n-hexane and ethyl acetate (70:30) as amobile phase. The spectroscopic data of the purified products were then compared with the available data bank of standard samples for their characterization. |
1: 10% 2: 85% | With dihydrogen peroxide In water; N,N-dimethyl-formamide at 20℃; for 0.0333333h; Green chemistry; chemoselective reaction; | |
1: 84% 2: 8% | With iodosylbenzene; C75H102Cl3Fe3N6O6 In dichloromethane at 20℃; for 15h; chemoselective reaction; | |
84% | With Ti(OCH(CH3)2)N(CH2C6H3C(CH3)3O)3; dihydrogen peroxide In methanol; water at 28℃; chemoselective reaction; | |
1: 5% 2: 80% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane 1.) 0 deg C, 2 h, 2.) RT, 12 h; | |
74% | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane at 25 - 28℃; for 2.5h; | |
1: 60% 2: 30% | With C19H13N3O4V; dihydrogen peroxide In methanol; dichloromethane at 0 - 4℃; for 2.5h; | Catalytic oxygenation of thioethers General procedure: To a solution of PhSMe (465 mg, 3.75 mmol) in methanol-dichloromethane (10:90 v/v), the catalyst [(L1)VO] (6.0 mg,0.015 mmol) and 50% H2O2 (1 mL) were added at 0 °C. The mixture was stirred for 2.5 h keeping the temperature at 0-4 °C. The solution was then dried in a vacuum. The products were isolated by thin layer chromatography (TLC). The solid PhSOMe and PhSO2Me were isolated as the third and second fractions, respectively, with yields of 187 mg and 222 mg, respectively. The products were characterised by IR spectroscopy. The results of the conversions of other thioethers to sulfoxides and sulfones are given in Table 2. |
1: 53% 2: 23% | With (Bu4N)2[{MoO(O2)2}2(μ-O)]; dihydrogen peroxide In acetonitrile for 3h; | Encouraged by the proficiency of 1 in the oxygenation of MPS,the catalytic performance of 1 was examined with additional substrateslisted in Chart 1 under the same conditions as those for theMPS reaction, and the results are collected in Table 1. Using oneequiv of H2O2, the reaction of BPS produced 53% sulfoxide and23% sulfone at 3 h, which indicates both a 100% utility of H2O2and lack of selectivity for sulfoxide. With 2.0 equiv of H2O2, BPSwas converted to the corresponding sulfone at 24 h. Compared tothe reactions of MPS and BPS, the reaction with PPS is significantlyslower, yielding 50% sulfoxide and 30% sulfone at 4 h. The reactionwith 4BT was slightly faster than that of MPS and resulted in 81%sulfoxide and 5% sulfone in 0.5 h (TOF: 910 h1). Lastly, PTEproceeded to 66% sulfoxide and 9% sulfone in 0.5 h for a TOF of660 h1. At 24 h, the reaction with PTE still contained 10% sulfoxidealong with 86% sulfone. This is possibly due to the conversionof PTE to the corresponding aldehyde as a minor side product |
1: 50% 2: 35% | With C36H27CuN8O2; dihydrogen peroxide In methanol; dichloromethane at 0℃; for 10h; | 2.8. General procedure for oxidation of organic thioethers General procedure: All the catalytic reactions were performed by a similar procedure.To a solution of 3 mmol of sulfide and 5 mL of 30% H2O2 in methanol-dichloromethane (1:9), 0.0120 mmol of catalyst 4a wasadded at 0 °C. The reaction mixture was stirred for 10 h. The solution was concentrated in a vacuum. The products were separatedby preparative TLC using benzene-acetonitrile (95:5) mixed solvent. Yields were determined by weighing the isolated products,which were characterized by 1H NMR and IR spectroscopy (Table 4). |
1: 21.7% 2: 50.4% | With dichloro(4,10-dimethyl-1,4,7,10-tetrazabicyclo[5.5.2]tetradecane)manganese(II); dihydrogen peroxide; calcium(II) trifluoromethanesulfonate In acetonitrile at 29.84℃; for 6h; | |
1: 30% 2: 48% | With C35H32ClCu2N2O7S2(1+)*ClO4(1-)*H2O; dihydrogen peroxide In methanol; dichloromethane at 0℃; for 2h; | 2.4 General procedure for the catalytic oxygenation of thioethers General procedure: Two catalytic reactions were performed by a similar procedure. To a solution of the catalyst [Cu2(L)(μ-OH)](ClO4)2 (0.0125 mmol) in methanol-dichloromethane (1:9) mixed solvent, 2.8 mmol of sulfide and 1mL of 50% H2O2 were added at 0 °C. The reaction mixture was stirred for 2 h. The solution was then dried in vacuum. The products were separated and purified by preparative TLC using benzene-acetonitrile (95:5) mixed solvent. The products were characterized by IR and 1H NMR spectra. |
1: 45% 2: 35% | With C19H15N3O4V; dihydrogen peroxide In methanol; dichloromethane; water at 0 - 4℃; for 0.5h; | |
1: 32% 2: 45% | With C19H14CuN4O; dihydrogen peroxide In methanol; dichloromethane at 0℃; for 6h; | 2.4. General procedure for catalytic oxygenation of thioethers General procedure: To the catalyst Cu(L) (0.014 mmol) dissolved in 10 mL dichloromethane-methanol (8:2) mixed solvent, 3 mmol of sulfide and 1.5mL of 50% H2O2 were all inserted in a 25 mL round-bottom flask at 0C. The mixture was stirred for 6 h. After the completion of the reaction the mixture was evaporated to dryness, water was addedand the product was extracted with dichloromethane. The organic layer was washed with brine, dried over Na2SO4, filtered. The products were separated and purified by preparative TLC using hexane-ethyl acetate (2:1) mixed solvent. The yields of the products obtained from all the reactions were determined after isolation,and characterized by1H NMR and IR spectra |
1: 35% 2: 8% | With cercosporin; oxygen In methanol at 20℃; Schlenk technique; Irradiation; Green chemistry; chemoselective reaction; | |
1: 15% 2: 5% | With Ir(ppy)<SUB>2</SUB>bpy; oxygen In methanol at 20℃; Irradiation; | 20 Example 1 Preparation of benzyl phenyl sulfoxide In a dry Shrek reaction tube,Add benzyl phenyl sulfide (0.25 mmol) sulfide in methanol (2.0 mL)PDI (0.5 mol%), PDI is a compound of formula A.Next, fill a balloon with oxygen and fix it on top of the Shrek reaction tube.The reaction was carried out at room temperature with a 15 W white CFL irradiation under a normal pressure of oxygen.After the reaction was completed, brine was added to the reaction.The aqueous phase was re-extracted with ethyl acetate.The synthesized organic extract was dried over Na 2 SO 4 and concentrated in vacuo.The residue obtained was separated by silica gel column chromatography ( petroleum ether: ethyl acetate = 10:1).Purification gave a white viscous solid (yield: 95%; selectivity: 100%). |
1: 1% 2: 93 % Spectr. | With dihydrogen peroxide In methanol; water at 25℃; for 24h; Title compound not separated from byproducts; | |
With urea-hydrogen peroxide In acetone at 20℃; for 2h; various catalysts, temp. and times; | ||
With buffer (pH 7.2-7.8); 3,3-dimethyldioxirane; bovine serum albumin at 4℃; for 3h; Yields of byproduct given; | ||
With buffer (pH 7.2-7.8); 3,3-dimethyldioxirane; bovine serum albumin at 4℃; for 3h; Yield given. Yields of byproduct given; | ||
With immobilized tungstate(IV) thermolysin; dihydrogen peroxide In <i>tert</i>-butyl alcohol at 40℃; for 24h; | ||
With iodosylbenzene In acetonitrile at 20℃; for 4h; Title compound not separated from byproducts.; | ||
1: 30.0 %Spectr. 2: 4.5 %Spectr. | With C68H72N4O6Ti2; dihydrogen peroxide In dichloromethane; water at 25℃; for 4.5h; enantioselective reaction; | |
With nitric acid In acetonitrile at 20℃; for 45h; chemoselective reaction; | ||
With C38H26N6NiS2(2+)*2NO3(1-); dihydrogen peroxide In water; acetonitrile at 20℃; | ||
With chloro-trimethyl-silane; dihydrogen peroxide In water; acetonitrile at 50℃; chemoselective reaction; | ||
With 1H-imidazole; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 1h; | ||
With dihydrogen peroxide In water at 20℃; | ||
With bis(acetylacetonate)oxovanadium; 2-{2-[2,2-dimethylcyclopent-3-enyl]-2-hydroxypropylideneamino}phenol; dihydrogen peroxide In dichloromethane; water at 20℃; for 2h; | ||
With (η5-C5H5)Mo(CO)3C2Ph; dihydrogen peroxide In acetonitrile at 60℃; for 2h; Inert atmosphere; Schlenk technique; | ||
With dihydrogen peroxide In methanol; water for 1h; | 2.4 Oxidation of benzyl phenyl sulfide to benzyl phenyl sulfoxide General procedure: A mixture of benzyl phenyl sulfide (1 g, 5.0 mmol), silica vanadic acid (5 mg, 0.039 mmol of V) and H2O2 30% (6 mmol) in CH3CN (3 mL) was stirred for 10 min. After completion of the reaction, solvent was evaporated and the product was extracted with ether (2× 10 mL), dried with anhydrous Na2SO4, filtered and evaporated to afford the crude sulfoxide product. Finally, the product was purified by column chromatography using ethyl acetate/hexane (1.5:8.5) as eluent to give benzyl phenyl sulfoxide as a white solid in 93% yield. | |
1: 87 %Spectr. 2: 13 %Spectr. | With C44Cl8F20N4Pd; oxygen In acetonitrile for 4h; UV-irradiation; | |
With 1H-imidazole; [(2-(2'-hydroxyphenyl)-5,6-dihydro-1,3-oxazine)2Mn(OAc)]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.0833333h; | 2.3. General procedure for sulfide oxidation General procedure: To a solution of sulfide (0.2 mmol), imidazole(ImH) (0.2 mmol) as axial ligand, chlorobenzene (0.2mmol) as internal standard, and [(N-O)2Mn(OAc)] (0.01 mmol) in a 1 : 1 mixture of CH3OH/CH2Cl2 (1 mL) was added 0.4 mmol UHP as oxidant. The mixture was stirred at room temperature and the reaction progress monitored by GC. Assignments of products were made by comparison with authentic samples. | |
Stage #1: Benzyl phenyl sulfide In methanol; dichloromethane at 20℃; for 0.166667h; Stage #2: With urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 2h; Overall yield = 66 %Chromat.; | 2.3.2. General procedure for oxidation of sulfides. A mixture of MPS (3mM), polymeric MoO2Salen complexes (0.005 mM) and (1 : 1) mixture of CH3OH/CH2Cl2 (2 mL) was stirred in a 5-mL tube for 10 min at room temperature. The oxidant UHP (3.75 mM) was then added, and the system was stirred at room temperature for approximately 2 h, and the reaction progress, was monitored by GC. Assignments of products were made bycomparison with authentic samples. All reactions were run at least in duplicate. | |
With dihydrogen peroxide In acetonitrile at 20℃; for 6h; | 2.5 General procedure for oxidation reaction General procedure: The liquid phase oxidation reactions were carried out in a two-necked round bottom flask fitted with a water condenser and placed in an oil bath at different temperatures under vigorous stirring for a certain period of time. Substrates (5 mmol) were taken in CH3CN solvent (5 mL) for different sets of reactions together with 2.5 × 10-2 mmol catalyst in which 10 mmol of H2O2 (30% in aq.) was added. Product analysis was performed using Varian 3400 gas chromatograph equipped with a 30 m CP-SIL8CB capillary column and a Flame Ionization Detector. All reaction products were identified by using Trace DSQ II GC-MS. | |
With [Fe(2-(2'-hydroxyphenyl)-2-thiazoline)2Cl]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.25h; Overall yield = 95 %Chromat.; | ||
With C10H10MoNO7; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.333333h; | 2.3. General procedure for sulfide oxidation General procedure: To a solution of sulfide (0.2 mM), chlorobenzene (0.2 mM) as internal standard and [MoO(O2)2(phox)] (0.015 mM) in a 1 : 1 mixture of CH3OH/CH2Cl2 (1 mL), 0.4mM UHP was added as the oxidant. The mixture was stirred at room temperature and the reaction progress was monitored by GC. Assignments of products were made by comparison with authentic samples. | |
With [Fe(phox)2Cl]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; | General procedure for sulfide oxidation General procedure: To a solution of sulfide (0.2mmol), chlorobenzene (0.2mmol) as internal standard and [Fe(phox)2Cl] (0.01mmol) in a 1:1 mixture of CH3OH/CH2Cl2 (1mL) was added 0.4mmol UHP as a oxidant. The mixture was stirred at room temperature and the reaction progress was monitored by GC. Assignments of products were made by comparison with authentic samples. | |
With Ru<SUB>2</SUB>(3-hydroxybenzoate)<SUB>4</SUB>Cl; dihydrogen peroxide In 1,2-dichloro-benzene; acetonitrile for 2h; | General procedure: To a solution of 1.25mmol of methyl phenyl sulfide in 25mL CH3CN, 1% catalyst A, B, or C was dissolved along with 1.0mmol 1,2 dichlorobenzene for internal standard. Initiating the reaction with 8.0equivalents of hydrogen peroxide was carried out by adding the hydrogen peroxide drop wise over about 30s. Samples were taken at the indicated times by removing 300μL of reaction mixture and quenching the hydrogen peroxide with about 5mg of MnO2. From this sample, 2μL of solution was injected into GC for analysis under the conditions described above. For catalyst D, the reactions were completed in the same fashion, except that water: acetone (3:2, v/v) was used as solvent. Reactions with other sulfides were carried out at the same concentrations as the MPS reactions above. However these reactions were scaled down to 10mL MeCN, 0.50mmol sulfide, 0.4mmol 1,2-dichlorobenzene, and 8equiv hydrogen peroxide. The reactions were sampled at the indicated times by quenching the unreacted hydrogen peroxide with MnO2 as above. Samples were analyzed via gas chromatography and percentages determined via standard curves for purchased sulfides and synthesized sulfoxides and sulfones. | |
With dihydrogen peroxide In acetonitrile at 20℃; for 0.25h; | ||
With 1-methyl-1H-imidazole; (S,S)-chloro[2,2'-[1,2-cyclohexanediylbis(nitrilomethylidyne)]bis-[4,6-bis(1,1-dimethylethyl)phenolato]](2-)-N,N',O,O'-manganese; dihydrogen peroxide In methanol at 20℃; for 0.333333h; | General procedure: Catalytic experiments were carried out as follows: the sulfide, the additive, and H2O2were added in this order to a solution of the catalyst in 1 mL of MeOH. The relative amountsare reported in the footnotes of the Tables. After the chosen time, the reaction was quenchedwith a saturated aqueous Na2SO3 solution (1 mL). The mixture was extracted with diethylether (4 × 5 mL) and the organic phase was dried over anhydrous Na2SO4. The solventwas removed under vacuum and the sample dissolved in CDCl3 for the 1H-NMR analysis. | |
With H3N*12H(1+)*[Mo36(NO)4O108(H2O)16](12-)*30.84H2O; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.5h; Green chemistry; | ||
With [iron(III)(acetylacetonato)(2-(2'-hydroxyphenyl)oxazoline)2]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.25h; | General procedure for sulfide oxidation General procedure: The following standard procedure was used for sulfide oxidation experiments. To a solution of sulfide (0.2 mmol), chlorobenzene (0.2 mmol) as internal standard and [Fe(phox)2(acac)] (0.01 mmol) in a 1:1 mixture of CH3OH/CH2Cl2 (1 mL), was added UHP (0.4 mmol). The mixture was stirred at room temperature, and the reaction progress was monitored by GC. Products were identified by comparison with authentic samples. | |
With dihydrogen peroxide In water; acetonitrile at 70℃; | General test for the oxidation General procedure: Sulfide oxidation studies were performed with dibenzylsulfide as the model reagent and with 35% w/v aq. H2O2as oxidant in the selected solvent, in a batch reactor under magnetic stirring at different temperatures, using the bulk and synthesized catalyst in homogeneous or heterogeneous conditions, respectively. The oxidation of dibenzylsulfide was typically carried out by heating asolution of 1 mmol (214 mg) of the substrate and 1 mmol% of bulkor supported catalyst in 5 mL of solvent, at the experiment temperatures (see tables). A variable amount of aqueous H2O235%w/v was used. The sample was collected from the mixture at time intervals. About 20 L of the reaction mixture was taken for each sample, which was then diluted in a mixture of H2O-CH2Cl2(2 mL).The CH2Cl2 layer was shaken with anhydrous Na2SO4. The reaction products were analyzed by gas chromatography using a Shimadzu 2010. The percentages of each compound in the reaction mixture were directly estimated from the corresponding chromatographic peak areas. The products were all known compounds and were identified by GC-MS using PerkinElmer equipment | |
With 1,5-diaminopentane tetrachloro mangenate; dihydrogen peroxide In water; acetonitrile at 40℃; for 5h; Green chemistry; | ||
With dihydrogen peroxide In methanol at 65℃; | ||
With C42H30Fe2N6O6*C2H6O; urea hydrogen peroxide adduct In acetonitrile at 20℃; for 0.25h; | 2.3. Catalytic sulfoxidation General procedure: 0.2 mmol UHP as an oxidant was added slowly to a stirringsolution of 1 ml of CH3CN containing the complex [Fe2(salcyn)3],a substrate (0.2 mmol) and chlorobenzene (0.2 mmol) as an internalstandard. Stirring was continued for 15 min at room temperaturein a closed system. The reaction progress was monitored by GC. Assignments of the products were made by comparison with authentic samples. | |
1: 90 %Chromat. 2: 10 %Chromat. | With dihydrogen peroxide In water at 25℃; for 0.5h; | 2.3. Procedure for oxidation of sulfides using MoO(O2)2Bipy-PMO-IL General procedure: In a typical experiment, methyl phenyl sulfide (0.2 mmol), H2O2(0.8 mmol), were added to 300 μL water in a reaction flask. Afterwards,the catalytic reaction was conducted by adding of MoO(O2)2Bipy-PMO-IL as the catalyst to the reaction mixture, then it was kept for vigorousstirring at room temperature for 30 min. After completion of thereaction, the catalyst filtered by centrifuge (3000 rpm, washed withmethanol and dichloromethane many times for next runs) and theproduct was extracted and identified by GC. |
With oxygen; methylene blue In ethanol at 20℃; for 0.0166667h; Irradiation; Flow reactor; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetra-n-propylammonium bromide In acetonitrile at 80℃; for 24h; | |
In N,N-dimethyl-formamide for 48h; Ambient temperature; Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 15% 2: 15% | With N-benzyl-N,N,N-triethylammonium chloride In tetrahydrofuran at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 25% 2: 31% 3: 30% | With potassium <i>tert</i>-butylate In tetrahydrofuran at -30 - 20℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 0.5h; | |
With n-butyllithium In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 1h; Stage #2: 1-benzoyl-1H-benzotriazole In tetrahydrofuran; hexane at -78 - 20℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium hydroxide In <i>tert</i>-butyl alcohol at 25℃; for 17h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 1h; Stage #2: 2-furoyl-1H-1,2,3-benzotriazole In tetrahydrofuran; hexane at -78 - 20℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 1h; Stage #2: 1-(1H-benzo[d][1,2,3]triazol-1-yl)-3-methylbutan-1-one In tetrahydrofuran; hexane at -78 - 20℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With sodium hydroxide; Bromotrichloromethane; Aliquat 336 In dichloromethane; water at 25℃; for 1h; | |
75% | With Bromotrichloromethane; sodium hydroxide In dichloromethane; water at 25℃; | |
65% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: With bromine at -78 - 20℃; for 10h; |
36% | Stage #1: Benzyl phenyl sulfone With lithium diisopropyl amide In tetrahydrofuran; diethyl ether; n-heptane; ethylbenzene at 20℃; for 1.5h; Inert atmosphere; Stage #2: With carbon tetrabromide In tetrahydrofuran; diethyl ether; n-heptane; ethylbenzene at 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 1h; Stage #2: p-chlorobenzoyl-1H-1,2,3-benzotriazole In tetrahydrofuran; hexane at -78 - 20℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With n-butyllithium In tetrahydrofuran; hexane; dimethyl sulfoxide at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With bis[2-(diphenylphosphino)phenyl] ether In dimethyl sulfoxide at 80℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; pentane at -78℃; for 1h; Stage #2: 1-(4'-methylbenzenesulfonyl)-1H-benzo[d][1.2.3]triazole In tetrahydrofuran; pentane at -78 - 20℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrabutylammomium bromide In water; acetone; toluene at 80 - 85℃; for 24h; | |
With tetrabutylammomium bromide In water; acetone; toluene at 85℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere; | One-Shot Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar were addedbenzyl sulfone (279 mg, 1.2 mmol) in dehydrated THF (12 mL), benzaldehyde (106 mg, 1.0 mmol)and diethyl chlorophosphate (207 mg, 1.2 mmol). A solution of lithium bis(trimethylsilyl)amide (1.3M in THF, 1.7 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 1 h and at 0 °C for additional 1 h. The reaction mixture was quenched with 5 mL of saturatedNH4Cl aq., and the organic and aqueous layers were separated. The organic layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to a flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (181 mg) in 56% yield. |
With potassium <i>tert</i>-butylate; 3,4-dihydronaphthalene-1(2H)-one In tetrahydrofuran Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With hydrogen In neat (no solvent) at 120℃; for 40h; | |
83% | With iodine; magnesium In methanol at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: Benzyl phenyl sulfone; p-(iodophenyl)carboxaldehyde With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1h; Stage #2: With diethyl chlorophosphate In tetrahydrofuran at 20℃; for 1h; Stage #3: With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; for 12h; Further stages.; | |
With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With 1,1'-bis-(diphenylphosphino)ferrocene In ethanol; water at 80℃; for 72h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 82 percent / NaH / dimethylformamide / 1 h / Ambient temperature 2: 72 percent / thionyl chloride / 3 h / Heating 3: 87 percent / 4 h / 105 - 110 °C / under nitrogen 4: NaH / dioxane / 20 h / Heating; under nitrogen 5: ethanol | ||
Multi-step reaction with 5 steps 1: 82 percent / NaH / dimethylformamide / 1 h / Ambient temperature 2: 72 percent / thionyl chloride / 3 h / Heating 3: 76 percent / 4 h / 105 - 110 °C / under nitrogen 4: NaH / dioxane / 20 h / Heating; under nitrogen 5: ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 56 percent / 1.) butyllithium, tetramethylethylenediamine; 2.) hexamethylphosphoric triamide / tetrahydrofuran / 1.) -78 deg C, 1 h; 2.) -78 deg C, 1h then rt., 5 h 2: 96 percent / sodium amalgam, disodium hydrogen phosphate / methanol / 0 deg C, 1 h then rt., 16 h 3: 81 percent / boron trifluoride*acetic acid / CHCl3 / 0.33 h / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 26% 2: 53.9% 3: 11% | With sodium hypochlorite In water; toluene at 20℃; for 3h; | 7 (Example 7); (Benzylthio)benzene (500 mg, 2.50 mmol) and cyanuric acid (32 mg, 0.25 mmol) were mixed with toluene (10 mL). 10% aqueous solution of sodium hypochlorite (5.57 g, 7.49 mmol) was added dropwise to the mixture at room temperature, and it was stirred for 3 hours. After that, sodium sulfite (315 mg, 2.50 mmol) and water (10 mL) were added to the reaction mixture, and it was extracted with ethyl acetate (10 mL). An organic layer was washed with water (5 mL) twice. The organic layer was concentrated under reduced pressure, and the obtained residue was subjected to purification by means of a silica gel column to obtain (benzylsulfinyl)benzene (138 mg, yield: 26%), [chloro(phenyl)methyl]sulfinyl}benzene (337 mg, yield: 53.9%) and (benzylsulfonyl)benzene (64 mg, yield: 11%). (Benzylsulfinyl)benzene: 1H-NMR (300MHz, CDCl3) δ 3.95-4.13 (2H, m), 6.95-7.01 (2H, m), 7.22-7.50 (8H, m) [Chloro(phenyl)methyl]sulfinyl}benzene: 1H-NMR (300MHz, CDCl3) δ 5.48 (1H, s), 6.89-7.50 (10H, m) (Benzylsulfonyl)benzene: 1H-NMR (300MHz, CDCl3) δ 4.31 (2H, s), 7.03-7.68 (10H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With N-(dicyclohexylphosphino)-2-(2'-methylphenyl)-1H-indole; palladium diacetate; lithium tert-butoxide In toluene at 110℃; for 12h; Inert atmosphere; | |
86% | With palladium diacetate; lithium tert-butoxide; XPhos at 120℃; for 12h; Inert atmosphere; | |
85% | Stage #1: methylphenylsulfonate With lithium hexamethyldisilazane In tetrahydrofuran at -20 - 20℃; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran at -20 - 20℃; for 1h; Inert atmosphere; Stage #3: bromobenzene With palladium diacetate; XPhos In tetrahydrofuran at 65℃; Degassed under vacuum; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | Stage #1: Benzyl phenyl sulfone With potassium hexamethylsilazane In tetrahydrofuran; toluene at -78℃; for 0.5h; Inert atmosphere; Stage #2: With oxygen In tetrahydrofuran; toluene at -78℃; Stage #3: With hydrogenchloride In water at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: diethyl chlorophosphate; lithium hexamethyldisilazane / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 2: dichlorobis(tri-O-tolylphosphine)palladium; copper(l) iodide; triethylamine / tetrahydrofuran / 70 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With N-(dicyclohexylphosphino)-2-(2'-methylphenyl)-1H-indole; potassium <i>tert</i>-butylate; palladium diacetate In 1,4-dioxane at 75℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In acetonitrile at 20℃; for 1.5h; Green chemistry; chemoselective reaction; | Synthesis of sulfoxides and sulfones General procedure: To a stirred suspension of the selected sulphide (10 mmol) andthe heterogeneous catalyst 4.2% VMIL(101) (0.1 g,∼2.5 mol%) inmethanol (10 ml), H2O2 (8 mmol) was added in one portion. Theslurry was stirred at room temperature for 20 min. The catalyst wasfiltered off and washed with methanol (10 ml). Ethyl acetate (10 ml)was added and resulting solution was dried with anhydrous sodiumsulphate and evaporated in vacuo to afford the crude product whichwas purified by column chromatography on silica gel (10% EtOAc inhexane) to afford the pure sulfoxide. Similar method was utilizedto produce sulfones. In this case 4 mol% of VMIL(101) in CH3CNwere utilized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With sodium hydride; nitrobenzene In tetrahydrofuran; mineral oil at 0℃; for 3h; Reflux; stereoselective reaction; | 4.2. A representative synthetic procedure of compounds 4a-aa and 5 General procedure: A representative synthetic procedure of compounds 4a-aa and 5 is as follows: sodium hydride (NaH, 60% in oil, 400 mg, 10.0 mmol) was added to a stirred solution of skeleton 3 (2.0 mmol) in THF (8 mL) at 0 °C. The resulting solution was stirred at 0 °C for 5 min and warmed to rt for 5 min. A solution of nitrobenzene (490 mg, 4.0 mmol) in THF (2 mL) was slowly added to the reaction mixtureat rt for 1 min. The reaction mixture was stirred at reflux for 3 h and cooled to rt. Water (1 mL) was added to the reaction mixture at 0 °C.The solvent was concentrated under reduced pressure. The resulting residue was diluted with water (10 mL) and the product mixture was extracted with CH2Cl2 (3 x 20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc 15:1 to 4:1) afforded compounds 4a-aa and 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium hydride; In tetrahydrofuran; mineral oil; at 67℃; for 3.0h;Inert atmosphere; | General procedure: NaH (100 mg, 60% in oil, 2.5 mmol) was added to a solution of sulfones 1 (0.5 mmol) in THF (8 mL). A solution of compounds 2 (0.5 mmol) in the THF (7 mL) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 3 h. The reaction mixture was cooled to rt. Water (1 mL) was added to the reaction mixture at 0 C. The solvent was concentrated under reduced pressure. The residue was diluted with water (10 mL) and the mixture was extracted with EtOAc (320 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc=10/1-6/1) afforded skeleton 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With platinum on carbon; potassium <i>tert</i>-butylate; hydrogen In toluene for 20h; Inert atmosphere; Reflux; | |
90% | With sodium hydride In mineral oil at 135℃; for 27h; Inert atmosphere; Schlenk technique; | |
81% | With sodium hydride at 135℃; for 5h; Inert atmosphere; |
70% | With C15H25Cl2N3NiO3; potassium <i>tert</i>-butylate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With sodium hydride In mineral oil at 135℃; for 28h; Inert atmosphere; Schlenk technique; | |
85% | With C15H25Cl2N3NiO3; potassium <i>tert</i>-butylate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere; | |
83% | With platinum on carbon; potassium <i>tert</i>-butylate; hydrogen In toluene for 24h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: acrolein In tetrahydrofuran at -78℃; for 2h; Inert atmosphere; | 1-phenyl-1-(phenylsulfonyl)but-3-en-2-yl acrylate (2) Two-step method: To a solutionof benzyl phenyl sulfone (300 mg, 1.29 mmol, 1.0 equiv.) in THF (6.5 mL) at -78 °C was added n-BuLi (1.6 M, 2.42 mL, 3.87 mmol, 3.0 equiv.) and the mixture was stirred for 1 h before adding acrolein (0.43 mL, 6.45 mmol, 5.0 equiv.) and stirring for 2 h. The reaction was quenched with water (20 mL) and extracted with MTBE (2 x 20 mL). The combined organic extracts were dried over MgSO4, filtered, and concentrated in vacuo. Purification by flash column chromatography on silica (4:1 to 1:1 hexanes:ethyl acetate) gave the corresponding hydroxysulfone (0.24 g, 64%) as an inseparable mixture of diastereomers. Spectral data for the mixture of diastereomers: IR (ATR): 3538, 3475, 1494, 1346, 1142,688 cm-1. 1H NMR (500 MHz, CDCl3) 7.59 (d, J = 7.7 Hz, 2H), 7.56-7.49 (m, 4H), 7.39-7.32 (m, 6H), 7.30-7.17 (m, 6H), 7.00 (d, J = 7.4 Hz, 2H), 5.69 (m, 1H), 5.54 (m, 1H), 5.35(d, J = 15.6 Hz, 1H), 5.31 (d, J = 15.0 Hz, 1H), 5.26 (d, J = 6.4 Hz, 1H),5.24 (d, J = 6.2Hz, 1H), 5.12 (d, J = 10.5, 1H), 5.05 (d, J = 10.4 Hz, 1H), 4.18 (s, 1H), 4.16 (d, J = 9.4Hz, 1H), 4.09 (d, J = 2.7 Hz, 1H), 3.19 (s, 1H). ). 13C NMR (125 MHz, CDCl3) 137.7,137.3, 136.2, 135.7, 133.9, 133.7, 131.3, 130.7, 130.4, 129.4, 128.9, 128.8, 128.7, 128.7,128.5, 128.4, 128.3, 117.9, 117.6, 76.5, 74.9, 71.1, 70.7. TOFMS (ES+): m/z calcd forC16H16O3SNa [M + Na]+: 311.0718; found: 311.0707. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With caesium carbonate In ethanol at 90℃; for 16h; Sealed tube; | 1-16 (Example 1) S-phenyl benzenesulfonothiolate (62.6 mg, 0.25 mmol) and cesium carbonate (Cs2CO3) as a thiosulfonate compound were dissolved in benzyl bromide (60 l, 0.50 mmol) and The mixture was added to the tube containing the seal (seal tube). To proceed the reaction, 0.5 ml (0.5 M) of ethanol (EtOH) was added and the vessel was closed and stirred at 90 ° C for 16 hours. The product was cooled and then diluted with dichloromethane (DCM) and filtered. The filtrate was concentrated by rotary evaporation and then the residue was purified by column chromatography (silica gel, 3% ethyl acetate in hexane) to produce the desired sulfones (sulfones). |
With caesium carbonate In ethanol at 90℃; for 16h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | Stage #1: 4-(3-oxo-1-propyn-1-yl)benzonitrile; Benzyl phenyl sulfone With diethyl chlorophosphate In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; Inert atmosphere; | 9 Example 9: Under a nitrogen atmosphere, 1 mmol of compound a3 and 1.2 mmol of compound b1 were mixed and dissolved in anhydrous tetrahydrofuran. 1.1 mmol of diethyl chlorophosphate was added and the reaction system was placed in an ice-water bath and stirred for 5 min. Plus 3.6 mmol of bis (trimethylsilyl) amide. The reaction was carried out at room temperature overnight. The saturated ammonium chloride solution was added, extracted with dichloromethane, washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and the solvent was removed. Column chromatography gave the title compound I in 77% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | Stage #1: Benzyl phenyl sulfone; 3-(3-oxoprop-1-yn-1-yl)benzonitrile With diethyl chlorophosphate In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; Inert atmosphere; | 10 Example 10: Under nitrogen protection,1 mmol of the compound a4 and 1.2 mmol of the compound b1 were mixed and dissolved in an anhydrous tetrahydrofuran solution,1.2 mmol of diethyl chlorophosphate was added and the reaction system was placed under ice-water bath,After stirring for 5 min, dropwise dropwise3.3 mmol bis (trimethylsilyl) amide.Reaction at room temperature overnight,Adding saturated ammonium chloride solution,Extracted with dichloromethane,Saturated sodium chloride solution,Dried over anhydrous magnesium sulfate,Filtering, removing the solvent,The title compound was obtained by column chromatography69%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: Benzyl phenyl sulfone; anthracen-9-yl-propynal With diethyl chlorophosphate In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; Inert atmosphere; | 11 Example 11: Under a nitrogen atmosphere, 1 mmol of compound a5 and 1.2 mmol of compound b1 were mixed and dissolved in an anhydrous tetrahydrofuran solution,1 mmol of diethyl chlorophosphate was added,The reaction system was placed under ice-water bath,After stirring for 5 min, 3 mmol of bis (trimethylsilyl) amide was added dropwise.Reaction at room temperature overnight,Adding saturated ammonium chloride solution,Extracted with dichloromethane,Saturated sodium chloride solution,Dried over anhydrous magnesium sulfate, filtered,Removing the solvent,The title compound K was obtained by column chromatography in 71% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: thiophen-2-yl-propynal; Benzyl phenyl sulfone With diethyl chlorophosphate In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; Inert atmosphere; | 12 Example 12: Under a nitrogen atmosphere, 1 mmol of compound a6 and 1.2 mmol of compound b1 were mixed and dissolved in anhydrous tetrahydrofuranRan the solution, add 1.1 mmol of diethyl chlorophosphate, the reaction system placed in ice water bath, stirring 5min drop by drop3 mmol of bis (trimethylsilyl) amine. The reaction was carried out at room temperature overnight, saturated ammonium chloride solution was added, extracted with methylene chloride and saturatedAnd washed with sodium chloride solution, dried over anhydrous magnesium sulfate, filtered to remove the solvent, and the column chromatography gave the title compound L, and the yield85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: Phenylpropargyl aldehyde; Benzyl phenyl sulfone With diethyl chlorophosphate In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With lithium hexamethyldisilazane In tetrahydrofuran at 20℃; Inert atmosphere; | 1 Example 1: Under a nitrogen atmosphere, 1 mmol of compound a1 and 1.2 mmol of compound b1 were mixed and dissolved in anhydrous tetrahydrofuranRan solution, 1 mmol of diethyl chlorophosphate was added and the reaction system was placed in an ice-water bath and stirred for 5 min.Bis (trimethylsilyl) amino lithium. The reaction was carried out overnight at room temperature, saturated ammonium chloride solution was added, extracted with dichloromethane, and saturated with chlorineSodium chloride solution, dried over anhydrous magnesium sulfate, filtered and the solvent was removed. Column chromatography gave the title compound A in 86% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: bromobenzene; 1,4-diazabicyclo [2.2.2] octane-1,4-diium-1,4-disulfinate With magnesium; lithium chloride In tetrahydrofuran at 20℃; for 1h; Flow reactor; Stage #2: benzyl bromide In tetrahydrofuran; N,N-dimethyl-formamide at 120℃; for 2h; Flow reactor; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; for 12h; Schlenk technique; Inert atmosphere; Glovebox; | |
90 % de | With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube; | General procedure: General procedure for closed system: To an oven dried 100 mL Schlenk flask in a N2glovebox, benzyl phenyl sulfone (464 mg, 2 mmol), KHMDS (410 mg, 2.05 mmol) and Ru-SNS (6.3mg, .01 mmol) were dissolved in 10 mL of Toluene. The alcohol or ester (1 mmol) was added to the reaction mixture, the vessel was sealed and stirred at 120oC for 12 hours. The reaction time was different for some cyclopropane entry as indicated.The reaction was allowed to cool to room temperature, then quenched with 5 mL of saturated NH4Cl solution. The mixture was extracted with 20 mL of Ethyl Acetate x3 and the organic layers were collected and dried over MgSO4. The solvent was concentrated under vacuum and purified by flash silica chromatography with a gradient of 100:0→88:12 (Hexane: Ethyl Acetate). Fractions where an overly large amount of minor diastereomer, byproduct, or starting material was present along with the desired product were discarded. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; for 12h; Schlenk technique; Inert atmosphere; Glovebox; | |
44% | With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; for 72h; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube; | General procedure: General procedure for closed system: To an oven dried 100 mL Schlenk flask in a N2glovebox, benzyl phenyl sulfone (464 mg, 2 mmol), KHMDS (410 mg, 2.05 mmol) and Ru-SNS (6.3mg, .01 mmol) were dissolved in 10 mL of Toluene. The alcohol or ester (1 mmol) was added to the reaction mixture, the vessel was sealed and stirred at 120oC for 12 hours. The reaction time was different for some cyclopropane entry as indicated.The reaction was allowed to cool to room temperature, then quenched with 5 mL of saturated NH4Cl solution. The mixture was extracted with 20 mL of Ethyl Acetate x3 and the organic layers were collected and dried over MgSO4. The solvent was concentrated under vacuum and purified by flash silica chromatography with a gradient of 100:0→88:12 (Hexane: Ethyl Acetate). Fractions where an overly large amount of minor diastereomer, byproduct, or starting material was present along with the desired product were discarded. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube; | General procedure: General procedure for closed system: To an oven dried 100 mL Schlenk flask in a N2glovebox, benzyl phenyl sulfone (464 mg, 2 mmol), KHMDS (410 mg, 2.05 mmol) and Ru-SNS (6.3mg, .01 mmol) were dissolved in 10 mL of Toluene. The alcohol or ester (1 mmol) was added to the reaction mixture, the vessel was sealed and stirred at 120oC for 12 hours. The reaction time was different for some cyclopropane entry as indicated.The reaction was allowed to cool to room temperature, then quenched with 5 mL of saturated NH4Cl solution. The mixture was extracted with 20 mL of Ethyl Acetate x3 and the organic layers were collected and dried over MgSO4. The solvent was concentrated under vacuum and purified by flash silica chromatography with a gradient of 100:0→88:12 (Hexane: Ethyl Acetate). Fractions where an overly large amount of minor diastereomer, byproduct, or starting material was present along with the desired product were discarded. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube; | General procedure for closed system: To an oven dried 100 mL Schlenk flask in a N2glovebox, benzyl phenyl sulfone (464 mg, 2 mmol), KHMDS (410 mg, 2.05 mmol) and Ru-SNS (6.3mg, .01 mmol) were dissolved in 10 mL of Toluene. The alcohol or ester (1 mmol) was added to the reaction mixture, the vessel was sealed and stirred at 120oC for 12 hours. The reaction time was different for some cyclopropane entry as indicated.The reaction was allowed to cool to room temperature, then quenched with 5 mL of saturated NH4Cl solution. The mixture was extracted with 20 mL of Ethyl Acetate x3 and the organic layers were collected and dried over MgSO4. The solvent was concentrated under vacuum and purified by flash silica chromatography with a gradient of 100:0→88:12 (Hexane: Ethyl Acetate). Fractions where an overly large amount of minor diastereomer, byproduct, or starting material was present along with the desired product were discarded. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ruthenium(bis[2‐(ethylsulfanyl)ethyl]amine)(dichloro)(triphenylphosphine); potassium hexamethylsilazane In toluene at 120℃; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube; | General procedure: General procedure for closed system: To an oven dried 100 mL Schlenk flask in a N2glovebox, benzyl phenyl sulfone (464 mg, 2 mmol), KHMDS (410 mg, 2.05 mmol) and Ru-SNS (6.3mg, .01 mmol) were dissolved in 10 mL of Toluene. The alcohol or ester (1 mmol) was added to the reaction mixture, the vessel was sealed and stirred at 120oC for 12 hours. The reaction time was different for some cyclopropane entry as indicated.The reaction was allowed to cool to room temperature, then quenched with 5 mL of saturated NH4Cl solution. The mixture was extracted with 20 mL of Ethyl Acetate x3 and the organic layers were collected and dried over MgSO4. The solvent was concentrated under vacuum and purified by flash silica chromatography with a gradient of 100:0→88:12 (Hexane: Ethyl Acetate). Fractions where an overly large amount of minor diastereomer, byproduct, or starting material was present along with the desired product were discarded. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With lithium hydroxide; In N,N-dimethyl-formamide; at 140℃; for 18h;Inert atmosphere; | General procedure: (1) adding a base, a benzylsulfonylbenzene compound, an aldehyde compound, and N,N-dimethylformamide (DMF) to the reaction vessel.And under argon protection;(2) after thoroughly mixing the reactants, heating;(3) purifying after the reaction to obtain a product;Among them, the base is CS2CO3, Na2CO3, NaHCO3, K2CO3, KHCO3, Li2CO3, CSOAc, KOH, LiOH, K3PO4,K2HPO4, CH3OONa, CF3COOK, CH3CH2ONa, t-BuOLi, t-BuONa, Et3N;Preferred Et3N;In order to achieve a better synthesis effect, preferred (benzylsulfonyl)benzene compounds, aldehyde compounds, and alkalis are preferred.The ratio is 1:1-10:0.1-0.2, and the optimal solution is preferably 1:8:0.16;The reaction temperature T is from 100 C to 160 C;It is preferably 140 C.It can be concluded from the synthesis reaction system of the above compound of the present invention that it is in Lewis base and N, N-diMethylformamide (as a solvent, a suitable amount, about 0.3ML to 1ML per mmol of benzylsulfonyl compound)Under the same action, a multi-component high-efficiency green formation of (benzyl)sulfonyl benzene compound and aldehyde compound (E)-(2-Technical solution of (phenylsulfonyl)vinyl)benzene and its derivatives. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With caesium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; for 24h; Inert atmosphere; Schlenk technique; | General procedure for the transition metal-free approach To a 50mL Schlenk tube containing benzylic ammonium salts (0.2mmol), p-toluenesulfonyl hydrazide (0.4mmol), Cs2CO3 (1.5mmol), and the tube was purged with N2 for 3 times, followed by 2mL of NMP. The resulted reaction mixture was allowed to stir for 24 h at 120°C under the atmosphere of nitrogen. After cooling to room temperature, the mixture was partitioned between water (15mL) and ethyl acetate (15mL). The phases were separated and the aqueous phase extracted with further ethyl acetate (3×15mL). The organic phases were dried over sodium sulfate. Filtration of the drying agent, and removal of all volatiles in vacuo gave a residue. Directly purified by flash chromatography to give the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: benzaldehyde In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #3: acetic anhydride In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; | Synthesis of l-Acetoxy-2-(phenylsulfonyl)-l,2-diphenylethane (2a) (representative) [Knowncompound].4 To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (232 mg, 1.0 mmol) and dehydrated THF (12 mL). Butyllithium(1.6 M in hexane, 0.59 mL, 1.1 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (0.13 g, 1.2 mmol) was added to the solution, and mixture was stirred for 30min. Acetic anhydride (0.13 g, 1.3 mmol) was added, and the mixture was stirred at -78 °C for 1 h.The reaction mixture was quenched with 5 mL of saturated NH4Cl aq., organic and aqueous layerswere separated. The aqueous layer was extracted with EtOAc, and combined organic layer was washed with water and brine. The combined organic layer was dried over MgSO4, and the solventswere removed under reduced pressure. The crude product was subjected to a flash chromatography(hexane/EtOAc, 7:3) to afford the desired acetoxy sulfone 2a (302 mg) in 79% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: m-bromobenzoic aldehyde In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #3: acetic anhydride In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; | Synthesis of l-Acetoxy-2-(phenylsulfonyl)-l,2-diphenylethane (2a) (representative) [Knowncompound].4 General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (232 mg, 1.0 mmol) and dehydrated THF (12 mL). Butyllithium(1.6 M in hexane, 0.59 mL, 1.1 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (0.13 g, 1.2 mmol) was added to the solution, and mixture was stirred for 30min. Acetic anhydride (0.13 g, 1.3 mmol) was added, and the mixture was stirred at -78 °C for 1 h.The reaction mixture was quenched with 5 mL of saturated NH4Cl aq., organic and aqueous layerswere separated. The aqueous layer was extracted with EtOAc, and combined organic layer was washed with water and brine. The combined organic layer was dried over MgSO4, and the solventswere removed under reduced pressure. The crude product was subjected to a flash chromatography(hexane/EtOAc, 7:3) to afford the desired acetoxy sulfone 2a (302 mg) in 79% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 4-bromo-benzaldehyde In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #3: acetic anhydride In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; | Synthesis of l-Acetoxy-2-(phenylsulfonyl)-l,2-diphenylethane (2a) (representative) [Knowncompound].4 General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (232 mg, 1.0 mmol) and dehydrated THF (12 mL). Butyllithium(1.6 M in hexane, 0.59 mL, 1.1 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (0.13 g, 1.2 mmol) was added to the solution, and mixture was stirred for 30min. Acetic anhydride (0.13 g, 1.3 mmol) was added, and the mixture was stirred at -78 °C for 1 h.The reaction mixture was quenched with 5 mL of saturated NH4Cl aq., organic and aqueous layerswere separated. The aqueous layer was extracted with EtOAc, and combined organic layer was washed with water and brine. The combined organic layer was dried over MgSO4, and the solventswere removed under reduced pressure. The crude product was subjected to a flash chromatography(hexane/EtOAc, 7:3) to afford the desired acetoxy sulfone 2a (302 mg) in 79% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: furfural In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #3: acetic anhydride In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; | Synthesis of l-Acetoxy-2-(phenylsulfonyl)-l,2-diphenylethane (2a) (representative) [Knowncompound].4 General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (232 mg, 1.0 mmol) and dehydrated THF (12 mL). Butyllithium(1.6 M in hexane, 0.59 mL, 1.1 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (0.13 g, 1.2 mmol) was added to the solution, and mixture was stirred for 30min. Acetic anhydride (0.13 g, 1.3 mmol) was added, and the mixture was stirred at -78 °C for 1 h.The reaction mixture was quenched with 5 mL of saturated NH4Cl aq., organic and aqueous layerswere separated. The aqueous layer was extracted with EtOAc, and combined organic layer was washed with water and brine. The combined organic layer was dried over MgSO4, and the solventswere removed under reduced pressure. The crude product was subjected to a flash chromatography(hexane/EtOAc, 7:3) to afford the desired acetoxy sulfone 2a (302 mg) in 79% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 3-thiophene carboxaldehyde In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #3: acetic anhydride In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; | Synthesis of l-Acetoxy-2-(phenylsulfonyl)-l,2-diphenylethane (2a) (representative) [Knowncompound].4 General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (232 mg, 1.0 mmol) and dehydrated THF (12 mL). Butyllithium(1.6 M in hexane, 0.59 mL, 1.1 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (0.13 g, 1.2 mmol) was added to the solution, and mixture was stirred for 30min. Acetic anhydride (0.13 g, 1.3 mmol) was added, and the mixture was stirred at -78 °C for 1 h.The reaction mixture was quenched with 5 mL of saturated NH4Cl aq., organic and aqueous layerswere separated. The aqueous layer was extracted with EtOAc, and combined organic layer was washed with water and brine. The combined organic layer was dried over MgSO4, and the solventswere removed under reduced pressure. The crude product was subjected to a flash chromatography(hexane/EtOAc, 7:3) to afford the desired acetoxy sulfone 2a (302 mg) in 79% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: m-bromobenzoic aldehyde In tetrahydrofuran; hexane for 0.5h; Inert atmosphere; Further stages; | One-Flask Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (465 mg, 2.0 mmol) and dehydrated THF (25 mL). Butyl lithium(1.6 M in hexane, 1.4 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (255 mg, 2.4 mmol) was added to the solution, and the mixture was stirred for30 min. Acetic anhydride (265 mg, 2.6 mmol) was added, and the mixture was stirred at -78 °C for 1h. Potassium tert-butoxide (269 mg, 2.4 mmol) was added, and the mixture was stirred at -78 °C for2 h and at 0 °C for additional 2 h. The reaction mixture was quenched with 5 mL of saturated NH4Claq., and the organic and aqueous layers were separated. The aqueous layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (319 mg) in 50% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 4-bromo-benzaldehyde In tetrahydrofuran; hexane for 0.5h; Inert atmosphere; Further stages; | One-Flask Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (465 mg, 2.0 mmol) and dehydrated THF (25 mL). Butyl lithium(1.6 M in hexane, 1.4 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (255 mg, 2.4 mmol) was added to the solution, and the mixture was stirred for30 min. Acetic anhydride (265 mg, 2.6 mmol) was added, and the mixture was stirred at -78 °C for 1h. Potassium tert-butoxide (269 mg, 2.4 mmol) was added, and the mixture was stirred at -78 °C for2 h and at 0 °C for additional 2 h. The reaction mixture was quenched with 5 mL of saturated NH4Claq., and the organic and aqueous layers were separated. The aqueous layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (319 mg) in 50% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere; | One-Shot Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar were addedbenzyl sulfone (279 mg, 1.2 mmol) in dehydrated THF (12 mL), benzaldehyde (106 mg, 1.0 mmol)and diethyl chlorophosphate (207 mg, 1.2 mmol). A solution of lithium bis(trimethylsilyl)amide (1.3M in THF, 1.7 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 1 h and at 0 °C for additional 1 h. The reaction mixture was quenched with 5 mL of saturatedNH4Cl aq., and the organic and aqueous layers were separated. The organic layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to a flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (181 mg) in 56% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere; | One-Shot Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar were addedbenzyl sulfone (279 mg, 1.2 mmol) in dehydrated THF (12 mL), benzaldehyde (106 mg, 1.0 mmol)and diethyl chlorophosphate (207 mg, 1.2 mmol). A solution of lithium bis(trimethylsilyl)amide (1.3M in THF, 1.7 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 1 h and at 0 °C for additional 1 h. The reaction mixture was quenched with 5 mL of saturatedNH4Cl aq., and the organic and aqueous layers were separated. The organic layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to a flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (181 mg) in 56% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: ortho-bromobenzaldehyde In tetrahydrofuran; hexane for 0.5h; Inert atmosphere; Further stages; | One-Flask Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (465 mg, 2.0 mmol) and dehydrated THF (25 mL). Butyl lithium(1.6 M in hexane, 1.4 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (255 mg, 2.4 mmol) was added to the solution, and the mixture was stirred for30 min. Acetic anhydride (265 mg, 2.6 mmol) was added, and the mixture was stirred at -78 °C for 1h. Potassium tert-butoxide (269 mg, 2.4 mmol) was added, and the mixture was stirred at -78 °C for2 h and at 0 °C for additional 2 h. The reaction mixture was quenched with 5 mL of saturated NH4Claq., and the organic and aqueous layers were separated. The aqueous layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (319 mg) in 50% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: Benzyl phenyl sulfone With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 4-chlorobenzaldehyde In tetrahydrofuran; hexane for 0.5h; Inert atmosphere; Further stages; | One-Flask Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar weresuccessively added benzyl sulfone (465 mg, 2.0 mmol) and dehydrated THF (25 mL). Butyl lithium(1.6 M in hexane, 1.4 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred for30 min. Benzaldehyde (255 mg, 2.4 mmol) was added to the solution, and the mixture was stirred for30 min. Acetic anhydride (265 mg, 2.6 mmol) was added, and the mixture was stirred at -78 °C for 1h. Potassium tert-butoxide (269 mg, 2.4 mmol) was added, and the mixture was stirred at -78 °C for2 h and at 0 °C for additional 2 h. The reaction mixture was quenched with 5 mL of saturated NH4Claq., and the organic and aqueous layers were separated. The aqueous layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (319 mg) in 50% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere; | One-Shot Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar were addedbenzyl sulfone (279 mg, 1.2 mmol) in dehydrated THF (12 mL), benzaldehyde (106 mg, 1.0 mmol)and diethyl chlorophosphate (207 mg, 1.2 mmol). A solution of lithium bis(trimethylsilyl)amide (1.3M in THF, 1.7 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 1 h and at 0 °C for additional 1 h. The reaction mixture was quenched with 5 mL of saturatedNH4Cl aq., and the organic and aqueous layers were separated. The organic layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to a flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (181 mg) in 56% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With diethyl chlorophosphate; lithium hexamethyldisilazane In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere; | One-Shot Synthesis of Ethenyl Sulfone 1a from Benzyl Sulfone (representative). General procedure: To a 50 mL of two-neck round-bottomed flask charged with a magnetic stirrer bar were addedbenzyl sulfone (279 mg, 1.2 mmol) in dehydrated THF (12 mL), benzaldehyde (106 mg, 1.0 mmol)and diethyl chlorophosphate (207 mg, 1.2 mmol). A solution of lithium bis(trimethylsilyl)amide (1.3M in THF, 1.7 mL, 2.2 mmol) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 1 h and at 0 °C for additional 1 h. The reaction mixture was quenched with 5 mL of saturatedNH4Cl aq., and the organic and aqueous layers were separated. The organic layer was extracted withEtOAc, and combined organic layer was washed with water and brine. The organic layer was driedover MgSO4, and the solvents were removed under reduced pressure. The crude product wassubjected to a flash chromatography (EtOAc/CH2Cl2/hexane, 1:1:8) and recrystallization (MeOH) toafford the desired ethenyl sulfone 1a (181 mg) in 56% yield. |
Tags: 3112-88-7 synthesis path| 3112-88-7 SDS| 3112-88-7 COA| 3112-88-7 purity| 3112-88-7 application| 3112-88-7 NMR| 3112-88-7 COA| 3112-88-7 structure
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H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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