A method for synthesizing α-aryl glucosinolates

Abstract

The invention provides a method for synthesizing alpha-aryl thioglycoside. The method includes steps that alpha-glycosyl thiol is used as a substrate in solvents N, N-dimethylformamide, tetrabutylammonium bromide is used as a ligand in the solvents, and the substrate and the ligand react to aryl iodide under the catalytic effects of copper iodide to obtain the alpha-aryl thioglycoside. Aryl halide directly reacts to thiophenol or thiol at one step under the catalytic effects of copper reagents to obtain coupled products, and the configuration of the original thiol can keep unchanged in procedures. The method has the advantages of mild conditions, high yield, inexpensive required reagents and the like.

Description

technical field

[0001] The invention belongs to the field of sugar chemical synthesis in organic chemistry, in particular to a method for preparing α-aryl glucosinolates. Background technique

[0002] Glucosinolates have been widely used in the synthesis of oligosaccharides. On the one hand, due to the good stability of glucosinolate donors, they can be used as donors and temporary protecting groups, and can also be converted into other donors; The activity of the glucosinolate donor can be regulated by the protecting group of the hydroxyl group on the sugar ring (especially 2- is the protecting group), the protecting group of the sulfur atom, the configuration of the glucosinolate and the reaction solvent, etc., therefore, the glucosinolate can be used Based on the "Armed-disarmed" strategy, the directional glycosylation between different glucosinolates is realized. Therefore, it is very important to efficiently synthesize glucosinolates in various configurations. [0003...

Examples

Embodiment 1

[0015] Example 1: Preparation of 6-O-hydroxyl-2,3,4-tri-O-benzyl-1-S-phenyl-α-D-glucose

[0016] The reaction formula is:

[0017]

[0018] At room temperature, add 16mg (10mol%) cuprous iodide, 177mg (0.8mmol) potassium phosphate, 42mg (0.13mmol) tetrabutylammonium bromide to a 50ml two-neck round bottom flask, vacuumize, and fill with nitrogen Three times, and then inject 0.47g (1mmol) α-glycosylthiol glucose and 0.17g (0.8mmol) iodobenzene solution dissolved in N,N dimethylformamide solvent into the circle with a disposable syringe under nitrogen protection. in the bottom flask. The round bottom flask was placed in an oil bath, and the temperature was raised to 80°C for 4 hours, and the reaction process was tracked by thin layer chromatography. After the reaction, cool down to room temperature, add saturated brine to the round bottom flask to quench the reaction, add an appropriate amount of saturated brine and ethyl acetate, extract and separate the liquids, combine t...

Embodiment 2

[0019] Example 2: Preparation of 6-O-hydroxyl-2,3,4-tri-O-benzyl-1-S-p-methylphenyl-α-D-glucose

[0020] The reaction formula is:

[0021]

[0022] At room temperature, add 16mg (10mol%) cuprous iodide, 177mg (0.8mmol) potassium phosphate, 42mg (0.13mmol) tetrabutylammonium bromide, 183mg (0.8mmol) in the two-neck round bottom flask of 50 milliliters 4-iodotoluene, evacuated, filled with nitrogen three times, and then injected 0.47g (1mmol) α-glycosylthiol glucose solution dissolved in N,N dimethylformamide solvent into in a round bottom flask. The round bottom flask was placed in an oil bath, and the temperature was raised to 80°C for 4 hours, and the reaction process was tracked by thin layer chromatography. After the reaction, cool down to room temperature, add saturated brine to the round bottom flask to quench the reaction, add an appropriate amount of saturated brine and ethyl acetate, extract and separate the liquids, combine the organic phases, and then dry with a...

Embodiment 3

[0023] Example 3: Preparation of 6-O-hydroxyl-2,3,4-tri-O-benzyl-1-S-p-nitrophenyl-α-D-glucose

[0024] The reaction formula is:

[0025]

[0026] At room temperature, add 16mg (10mol%) cuprous iodide, 1177mg (0.8mmol) potassium phosphate, 42mg (0.13mmol) tetrabutylammonium bromide, 209mg (0.8mmol) in the two-neck round bottom flask of 50 milliliters 4-iodotoluene, evacuated, filled with nitrogen three times, and then injected 0.47g (1 mmol) of α-glycosylthiol glucose solution dissolved in N,N dimethylformamide solvent into in a round bottom flask. The round bottom flask was placed in an oil bath, and the temperature was raised to 80°C for 4 hours, and the reaction process was tracked by thin layer chromatography. After the reaction, cool down to room temperature, add saturated brine to the round bottom flask to quench the reaction, add appropriate amount of saturated brine and ethyl acetate, extract and separate the liquids, combine the organic phases, and then dry with ...

technical field

[0001] The invention belongs to the field of sugar chemical synthesis in organic chemistry, in particular to a method for preparing α-aryl glucosinolates. Background technique

[0002] Glucosinolates have been widely used in the synthesis of oligosaccharides. On the one hand, due to the good stability of glucosinolate donors, they can be used as donors and temporary protecting groups, and can also be converted into other donors; The activity of the glucosinolate donor can be regulated by the protecting group of the hydroxyl group on the sugar ring (especially 2- is the protecting group), the protecting group of the sulfur atom, the configuration of the glucosinolate and the reaction solvent, etc., therefore, the glucosinolate can be used Based on the "Armed-disarmed" strategy, the directional glycosylation between different glucosinolates is realized. Therefore, it is very important to efficiently synthesize glucosinolates in various configurations. [0003...

Examples

Embodiment 1

[0015] Example 1: Preparation of 6-O-hydroxyl-2,3,4-tri-O-benzyl-1-S-phenyl-α-D-glucose

[0016] The reaction formula is:

[0017]

[0018] At room temperature, add 16mg (10mol%) cuprous iodide, 177mg (0.8mmol) potassium phosphate, 42mg (0.13mmol) tetrabutylammonium bromide to a 50ml two-neck round bottom flask, vacuumize, and fill with nitrogen Three times, and then inject 0.47g (1mmol) α-glycosylthiol glucose and 0.17g (0.8mmol) iodobenzene solution dissolved in N,N dimethylformamide solvent into the circle with a disposable syringe under nitrogen protection. in the bottom flask. The round bottom flask was placed in an oil bath, and the temperature was raised to 80°C for 4 hours, and the reaction process was tracked by thin layer chromatography. After the reaction, cool down to room temperature, add saturated brine to the round bottom flask to quench the reaction, add an appropriate amount of saturated brine and ethyl acetate, extract and separate the liquids, combine t...

Embodiment 2

[0019] Example 2: Preparation of 6-O-hydroxyl-2,3,4-tri-O-benzyl-1-S-p-methylphenyl-α-D-glucose

[0020] The reaction formula is:

[0021]

[0022] At room temperature, add 16mg (10mol%) cuprous iodide, 177mg (0.8mmol) potassium phosphate, 42mg (0.13mmol) tetrabutylammonium bromide, 183mg (0.8mmol) in the two-neck round bottom flask of 50 milliliters 4-iodotoluene, evacuated, filled with nitrogen three times, and then injected 0.47g (1mmol) α-glycosylthiol glucose solution dissolved in N,N dimethylformamide solvent into in a round bottom flask. The round bottom flask was placed in an oil bath, and the temperature was raised to 80°C for 4 hours, and the reaction process was tracked by thin layer chromatography. After the reaction, cool down to room temperature, add saturated brine to the round bottom flask to quench the reaction, add an appropriate amount of saturated brine and ethyl acetate, extract and separate the liquids, combine the organic phases, and then dry with a...

Embodiment 3

[0023] Example 3: Preparation of 6-O-hydroxyl-2,3,4-tri-O-benzyl-1-S-p-nitrophenyl-α-D-glucose

[0024] The reaction formula is:

[0025]

[0026] At room temperature, add 16mg (10mol%) cuprous iodide, 1177mg (0.8mmol) potassium phosphate, 42mg (0.13mmol) tetrabutylammonium bromide, 209mg (0.8mmol) in the two-neck round bottom flask of 50 milliliters 4-iodotoluene, evacuated, filled with nitrogen three times, and then injected 0.47g (1 mmol) of α-glycosylthiol glucose solution dissolved in N,N dimethylformamide solvent into in a round bottom flask. The round bottom flask was placed in an oil bath, and the temperature was raised to 80°C for 4 hours, and the reaction process was tracked by thin layer chromatography. After the reaction, cool down to room temperature, add saturated brine to the round bottom flask to quench the reaction, add appropriate amount of saturated brine and ethyl acetate, extract and separate the liquids, combine the organic phases, and then dry with ...

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