亚甲基环丁烷硼酯的合成和转化(太实用)

文摘   2024-11-14 08:55   四川  

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背景介绍

首先,抛出一个问题:亚甲基环丁烷硼酯怎么比较简单的合成得到?不知道的可以私信小编获取。

亚甲基环丁烷硼酯的转化非常之多,这些对于合成含有环丁烷结构的分子非常实用,同样,其它硼酸酯的转化大家也可以参考。

图片来源:Chem. Sci.

实验操作

图片来源:Chem. Sci.

To a 5-mL screw-up vial were added 2f (60 mg, 0.20 mmol), Cu2O (2.8 mg, 20 μmol), KI (166 mg, 1.00 mmol), 25% NH3•H2O (38 μL, 0.50 mmol of NH3) and H2O (1.0 mL). The mixture was stirred at rt for 24 h under air. After the reaction was completed, all volatiles were evaporated and the residue was purified by column chromatography on silica gel (hexane:EA 50:1) to give the product 6 (27.6 mg, 46%) as a colorless oil.


图片来源:Chem. Sci.

To a solution of CuBr2 (66 mg, 0.30 mmol) in MeOH/H2O (1:1) (1.0 mL) was added 2f (30 mg, 0.10 mmol), and the resulting reaction mixture was stirred for 24 h at 80 °C. After the mixture was cooled to room temperature, the volatiles were evaporated under reduced pressure, and the residue was purified by column chromatography on silica gel (hexane:EA 50:1) to give the product 7 (18.6 mg, 74%) as a colorless oil.


图片来源:Chem. Sci.

To a solution of sodium perborate tetrahydrate (154 mg, 1.00 mmol) in THF/H2O (1:1) (2.0 mL) was added 2f (60 mg, 0.20 mmol), and the resulting reaction mixture was stirred for 3h at room temperature. After the mixture was completed, the volatiles were evaporated under reduced pressure, and the residue was purified by column chromatography on silica gel (hexane:EA 20:1) to give product 9 (25.1 mg, 66%) as a mixture of two inseparable diastereoisomers (d.r. = 1:1).


图片来源:Chem. Sci.

To a 5-mL screw-up vial were added 2f (30 mg, 0.10 mmol) and DCM (1.0 mL). The flask was evacuated and backfilled with O3 from a balloon for three times, and the resulting reaction mixture was stirred 0.5 h at -78 °C. After the reaction was quenched with PPh3, the volatiles were evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane:EA 30:1) to give the product 16 (13.0 mg, 74%).


图片来源:Chem. Sci.

To a 5-mL vial were added 2f (60 mg, 0.20 mmol), NaN3 (20 mg, 0.30 mmol), Cu(OAc)2 (3.6 mg, 0.020 mmol), and MeOH (1.0 mL), and the resulting reaction mixture was stirred at 55 °C under air for 3 h. After the reaction mixture was cooled to room temperature, the volatiles were evaporated  under reduced pressure, and the residue was purified by column chromatography on silica gel (hexane:EA 100:1) to give the product 10 (31.8 mg, 74%) as a yellow oil.


图片来源:Chem. Sci.

To a 5-mL screw-up vial were added 2h (30.4 mg, 0.100 mmol), Cu(OAc)2 (22 mg, 0.11 mmol), morpholine (11 μL, 0.10 mmol), acetonitrile (0.5 mL) and D2O (30 μL). The mixture was allowed to stir at 80 °C for 16 h under Ar. After the reaction mixture was cooled to room temperature, the volatiles were evaporated under reduced pressure, and the residue was purified by column chromatography on silica gel (hexane:EA 100:1) to give the product 13 (9.8 mg, 55%) as a colorless oil.


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