醇氧化成醛的反应

产物官能团类型

1. DMP氧化

Dess-Martin高碘化物氧化是一种温和的氧化反应，反应只需要在室温下氧化数小时，较为常用的溶剂是二氯甲烷

案例1



To a solution of the SM (1.0 equiv) in DCM (0.1 M) was added Dess-Martin periodinane (1.8 equiv). The mixture was stirred at RT for 16 h, after which time it was poured into EtOAc (800 mL), washed with 1:1 10% Na2S2O3/sat aq NaHCO3 (4x), then sat aq NaCl. The org layer was dried (MgSO4) and concentrated in vacuo to provide to product as a yellow solid. [96%]


[Patent Reference: WO2010026121, page 33


Example 2



To a solution of the SM (1.30 g, 4.57 mmol) in DCM (200 mL) was added Dess-Martin periodinane(3.88 g, 9.15 mmol). The reaction mixture was stirred at RT for 3 h, after which time it was quenched with 20% aq Na2S2O3(20 mL) and sat aq NaHCO3 (80 mL). The mixture was stirred until the aq layer was clear. The aq layer was extracted with DCM (3 x 50 mL). The combined organics were dried Na2SO4) and concentrated to provide the product as a yellow oil. [1.25 g, 97%]


[Patent Reference: WO2014177977, page 75


2. Swern氧化

Swern氧化是一种较为温和的氧化反应，反应需要在低温下（-78 °C）滴加相关的试剂，并且缓慢升高到室温。但是该反应会产生二甲硫醚， 是一种非常不友好的含硫化合物，气味难闻。

案例1

To a stirred solution of (COCl)2 (0.49 mL, 5.5 mmol) in DCM (12 mL) was slowly added DMSO (0.79 mL, 11.0 mmol) at -78 °C. The resulting mixture was stirred at -78 °C for 30 min. To the mixture was slowly added a solution of the SM (845 mg, 5.0 mmol) in DCM (10 mL) over 10 min, followed by the dropwise addition of TEA (3.1 mL, 22.5 mmol). The reaction mixture was slowly allowed to warm to 25 °C. The mixture was stirred 1 h at 25 °C, after which time it was quenched with H2O (10 mL). The mixture was extracted with DCM (3 x 20 mL). The combined organics were washed with 1M HCl (10 mL), sat aq Na2CO3, brine, dried (Na2SO4), and concentrated. The resulting material was purified by silica gel column chromatography (2:1 PE/EtOAc) to provide the product as an off-white solid. [600 mg, 72%]

[Patent Reference: WO2016011390, page 112

3. 二氧化锰氧化

二氧化锰是一种温和氧化剂，常用来氧化烯丙基或者苄醇到相应的醛

案例1

A mixture of the SM (0.129 g, 0.313 mmol), MnO2 (0.807 g, 9.28 mmol), and dry DCM was stirred at RT for 16 h. The mixture was filtered through celite and the filtrate was concentrated in vacuo to provide the product as a colorless oil which was used in the next step without additional purification. [0.113 g, 86%]

UK Pat App GB2463151A, page 125