DMSO 可由各种亲电试剂（E）活化后与醇反应，生成烷氧基硫盐，接着发生消除，生成醛或酮。
常用的亲电试剂有 DCC，(CH 3 CO) 2 O， (CF 3 CO) 2 O， SOCl 2 ，(COCl) 2 等.
1、DMSO-DCC 氧化
将 DCC 溶于 DMSO 中，然后加入醇与氢受体而进行氧化反应，氢的给予体可用磷酸、三氟醋酸、吡啶-磷酸、吡啶-三氟醋酸等。该方法广泛用于对酸敏感保护基保护的糖类的氧化，反应一般在室温进行，比较方便，但缺点是出去氧化副产物尿素衍生物比较困难。此时则用 Swern 氧化法较为方便。
DMSO-DCC 氧化法示例：
Cholane-24-ol (1.033 g., 3 mmoles) is dissolved by gentle warming in 10 ml. of anhydrous benzene in a 50-ml. flask, and 10 ml. of rigorously dried dimethyl sulfoxide is added. To the clear solution are added 0.24 ml. (3.0 mmoles) of anhydrous pyridine, 0.12 ml. (1.5 mmoles) of distilled trifluoroacetic acid, and 1.85 g. (9 mmoles) of dicyclohexylcarbodiimide, in that order. The flask is tightly stoppered and left at room temperature for 18 hours. Benzene (30 ml.) is then added, and the crystalline dicyclohexylurea is removed by filtration and washed with benzene. The combined filtrates and washings are extracted three times with 50-ml. portions of water to remove the dimethyl sulfoxide. The organic layer is dried with sodium sulfate and evaporated to dryness under reduced pressure. There is obtained 2.12 g. of syrup which partially crystallizes. Thin-layer chromatography of this material shows a very intense spot of cholane-24-al, traces of starting material, and two compounds near the solvent front as well as excess carbodiimide. The crude product is dissolved in benzene-hexane (1:1) and applied to a column containing 125 g. of silicic acid. Elution with the same solvent gives traces (less than 5 mg. each) of the two fast-moving components in fractions 2 and 4 (125-ml. fractions) and chromatographically pure cholane-24-al in fractions 5–8. Evaporation of the pooled fractions yields 870 mg. (84%) of the pure crystalline aldehyde, m.p. 102–104°. Recrystallization from 5 ml. of acetone raises the melting point to 103–104°. The compound gives a crystalline 2,4-dinitrophenylhydrazone, m.p. 163–164°, from ethanol.
MOFFA 氧化法（使用 POLYMERIC CARBODIIMIDE）实例
A 250-ml., three-necked, round-bottomed flask equipped with a mechanical stirrer, a gas-inlet, and a stopper is charged with 540 mg. (0.00346 mole) of a mixture of cis- and trans-4-tert-butylcyclohexanols, 50 ml. of anhydrous benzene, and 25 ml. of anhydrous dimethyl sulfoxide. While a slight positive pressure of argon is maintained in the system, 13.19 g. of carbodiimide resin is added, followed by 0.2 ml. of dimethyl sulfoxide containing 98 mg. (0.0010 mole) of anhydrous orthophosphoric acid. The resulting mixture is stirred at room temperature for 3.5 days. The beads are then separated by filtration and washed with three 100-ml. portions of diethyl ether, and the combined filtrates are washed with five 100-ml. portions of water. After evaporation of the organic phase to dryness, the residue crystallizes, providing 446–450 mg. (83–84%) of crude 4-tert-butylcyclohexanone, m.p.42–45°. The deactivated carbodiimide resin can be regenerated by treatment with triethylamine and 4-toluenesulfonyl chloride.
DMSO-(COCl) 2 氧化（Swern Oxidation or Moffatt-Swern Oxidation ）
各种酰氯及亚硫酰氯作为DMSO的活化剂是有效的，而由草酰氯活化的DMSO对醇的氧化最为合适。反应中生成的过渡中间体烷氧基硫盐不稳定，反应需要在低温下进行（温度一般在-60° C以下）。
DMSO-(COCl) 2 氧化示例
A 250-mL, three-necked, round-bottomed flask, containing a magnetic stirring bar is equipped with a low-temperature thermometer and two equalizing dropping funnels. One of these is connected to a nitrogen flow line and is charged with a solution of N-Boc-L-serinol (8.0 g, 34.6 mmol) in methylene chloride (60 mL), the other is charged with a solution of dimethyl sulfoxide (8.10 g, 103.71 mmol) in 10 mL of dried methylene chloride. The flask is charged with a solution of oxalyl chloride (6.58 g, 51.9 mmol) in 80 mL of methylene chloride, then cooled to −78°C in a CryoCool bath. When the solution in the flask is at −78°C, dimethyl sulfoxide is added dropwise over 25 min, while the temperature of the reaction mixture rises to −70°C. At the end of the addition the reaction solution is warmed to −60°C over a period of 20 min, then the N-Boc-L-serinol is added dropwise over 50 min and the reaction temperature rises to −55°C. The dropping funnel is washed with two 5-mL portions of methylene chloride, then charged with a solution of N,N-diisopropylethylamine (36 mL, 200 mmol) in 5 mL of methylene chloride and the reaction solution is warmed to −45°C over a period of 30 min. N,N-Diisopropylethylamine is added over 5 min, then the reaction flask is removed from the CryoCool bath and allowed to warm to 0°C over 10 min. The reaction solution is transferred to a 500-mL separatory funnel charged with 130 mL of ice-cold 1 M hydrochloric acid solution. The two phases are separated, the aqueous phase is extracted with methylene chloride (3 × 30 mL), and the combined organic phases are washed with pH 7 aqueous phosphate buffer (4 × 80 mL), then dried with anhydrous sodium sulfate and concentrated under reduced pressure to give 7.89 g (99% crude yield) of the aldehyde as a clear yellow oil. Analysis of crude aldehyde by 1 H NMR indicates a chemical purity of >95%.
DMSO-Cl 2 ， DMS-NCS （Corey-Kim 氧化）
用 DMSO-Cl 2 和 DMS-NCS 体系使醇氧化虽已广泛应用且收率也高，但还是以DMSO-(COCl) 2 氧化较为方便。
Corey-Kim 氧化示例：
A 1-l., three-necked, round-bottomed flask equipped with a mechanical stirrer, a thermometer, a dropping funnel, and an argon-inlet tube is charged with 8.0 g. (0.060 mole) of N-chlorosuccinimide and and 200 ml. of toluene. While a continuous positive argon pressure is maintained, the solution is stirred and cooled to 0°, and 6.0 ml. (0.10 mole) of methyl sulfide is added. A white precipitate appears immediately after addition of the sulfide. The mixture is cooled to −25° using a carbon tetrachloride-dry ice bath, and a solution of 6.24
g. (0.0400 mole) of 4-tert-butylcyclohexanol (mixture of cis- and trans-) in 40 ml. of toluene is added dropwise over 5 minutes. The stirring is continued for 2 hours at −25°before a solution of 6.0 g. (0.59 mole) of triethylamine in 10 ml. of toluene is added dropwise over 3 minutes. The cooling bath is removed; after 5 minutes 400 ml. of diethyl ether is added. The organic layer is washed with 100 ml. of 1% hydrochloric acid, then with two 100-ml. portions of water, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The residue is transferred to a 50-ml., round-bottomed flask and distilled bulb to bulb at 120° (25 mm.), yielding 5.54–5.72 g. (90–93%) of 4-tert-butylcyclohexanone, m.p. 41–45°.
DMSO-SO 3 -Pyridine
The combination of DMSO with S0 3 -pyridine complex in the presence of triethylamine yields a reagent that rapidly oxidizes primary and secondary alcohols in good yield at room temperature to aldehydes and ketones, respectively. An attractive feature of this reagent is its property of effecting oxidation of allylic alcohols to the corresponding unsaturated carbonyl compounds. The S0 3 -pyridine complex in DMSO can be used to oxidize acid-labile trans-diols or cis-diols to quinones. This reagent has also been used to oxidize alkaloid hydroxyl groups to ketone groups. Application of the DMSO-S0 3 -pyridine reagent to partially acetylated carbohydrates leads to oxidation as well as elimination of the elements of acetic acid, thus providing a high yield to novel unsaturated carbohydrates.
DMSO-SO 3 -Pyridine氧化反应示例
In anhydrous dimethyl sulfoxide (75 ml) were dissolved, 1,2,3,4-tetramethoxy-5-methyl-6- (4-hydroxybutyl)benzene (14.2 g, 50 mmole) and triethylamine (56.0 ml), and the solution was stirred at room temperature; A solution of sulfur trioxide pyridine complex (31.8 g, 200 mmole) in anhydrous dimethyl sulfoxide (75 ml) was added dropwise to the solution over a 25-minute period, followed by stirring at room temperature for 35 minutes..; The reaction solution was poured into ice-water (300 g), and the product was extracted with isopropyl ether (500 ml)..; The isopropyl ether layer was washed with 10percent aqueous phosphoric acid solution and aqueous sodium chloride solution, successively, and dried (over MgSO4), and the solvent was distilled off..; The residue was distilled under reduced pressure, thereby yielding 1,2,3,4-tetramethoxy-5-methyl-6-(3-formylpropyl)-benzene (11.3 g, 80%, bp 137. to 140.℃.0.7mmHg).
