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Method for constructing sterides-6beta, 7beta-methylene structure by cascade reaction

A tandem reaction and methylene technology, which is applied in the direction of chemical instruments and methods, steroids, steroids, etc., can solve the problems of expensive reaction reagents, many reaction steps, long reaction steps, etc., and achieve cheap raw materials and short reaction steps. The effect of less and simple operation

Inactive Publication Date: 2014-03-26
XIAN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] CN101177446A has reported a new method for stereoselectively synthesizing 6β by Winstein cyclopropanation method, 7β-methylene structure, but this method still needs 7-position allylic oxidation, and reaction reagent is expensive, reaction step is long, and total Low yield, etc.
However, there are still many reaction steps

Method used

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  • Method for constructing sterides-6beta, 7beta-methylene structure by cascade reaction
  • Method for constructing sterides-6beta, 7beta-methylene structure by cascade reaction
  • Method for constructing sterides-6beta, 7beta-methylene structure by cascade reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Synthesis of compound 3β-acetoxy-6β,7β; 15β,16β-dimethylene-5α-androst-5-ol-17-one:

[0023] At room temperature, to ether (100mL ) solution, add cuprous iodide (762mg, 4.0mmol) and montmorillonite K-10 (300mg), stir for 0.5h to 1h, then add Zn-Cu preparation (2.8g), diiodomethane (3.2mL). Raise the temperature to 65°C-70°C, and keep it warm for 4 hours. After the reaction was completed, cool down to room temperature, add dichloromethane (100mL) to dilute, wash with saturated ammonium chloride aqueous solution and water successively, dry over anhydrous magnesium sulfate, separate by suction filtration, and remove the solvent by extraction under reduced pressure to obtain an oily substance. Column separation (V 石油醚 / V 乙酸乙酯 =1:2), remove the solvent under reduced pressure, and obtain the target compound 3β-acetoxy-6β, 7β after vacuum drying at 40°C; 15β, 16β-dimethylene-5α-androst-5-ol-17-one , off-white powder, 834mg (83%, 2.2mmol).

[0024] In this example, the sta...

Embodiment 2

[0026] Synthesis of compound 3β-acetoxy-6β,7β; 15β,16β-dimethylene-5α-androst-5-ol-17-one:

[0027] At room temperature, diethyl ether (100mL ) solution was added cuprous iodide (762mg, 4.0mmol), lithium bromide (300mg) and lithium carbonate (300mg), stirred for 0.5h and added Zn-Cu preparation (2.8g), diiodomethane (3.2mL). Raise the temperature to 65°C-70°C, and keep it warm for 4 hours. After the reaction was completed, cool down to room temperature, add dichloromethane (100mL) to dilute, wash with saturated ammonium chloride aqueous solution and water successively, dry over anhydrous magnesium sulfate, separate by suction filtration, and remove the solvent by extraction under reduced pressure to obtain an oily substance. Column separation (V 石油醚 / V 甲醇 =1:2), remove the solvent under reduced pressure, and obtain the target compound 3β-acetoxy-6β, 7β after vacuum drying at 40°C; 15β, 16β-dimethylene-5α-androst-5-ol-17-one , off-white powder, 894mg (89%, 2.4mmol).

[002...

Embodiment 3

[0030] Synthesis of compound 3β-benzoyloxy-6β,7β; 15β,16β-dimethylene-17α-pregna-5α-ol-21,17-carboxylide:

[0031]At room temperature, 3β, 7α-dibenzoyloxy-5α, 6α-epoxy-15β, 16β-methylene-17α-pregna-21, 17-carboxylide (1.0g, 1.6mmol) in ether (100mL) solution, add cuprous iodide (462mg) and titanocene chloride (100mg), stir for 0.5h to 1h, then add Zn-Cu preparation (1.8g), elemental iodine (20mg), Diiodomethane (1.8 mL). Raise the temperature to 75°C-80°C, and keep it warm for 5 hours. After the reaction was completed, cool down to room temperature, add dichloromethane (100mL) to dilute, wash with saturated ammonium chloride aqueous solution and water successively, dry over anhydrous magnesium sulfate, separate by suction filtration, and remove the solvent by extraction under reduced pressure to obtain an oily substance. Column separation (V 石油醚 / V 乙酸乙酯 =1:2), the solvent was removed under reduced pressure, and the target compound 3β-benzoyloxy-6β, 7β was obtained after va...

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Abstract

The invention discloses a method for constructing a sterides-6beta, 7beta-methylene structure by a cascade reaction, which comprises the following step that: a 3beta-R3O-5alpha-hydroxy-6beta, 7beta-sterides compound is prepared by the cyclomethylenation reaction of a 3beta-R3O-7alpha-R7-5appha, 6alpha-epoxy-sterides compound serving as a raw material and a methylenation reagent under the complexing action of an inorganic metal salt or an organic metal compound and the initiation action of an initiator. The method has the advantages of readily available materials, fewer reaction steps, simplicity of operation, high stereoselectivity for constructing the 6beta, 7beta-methylene structure unit and high yield of target compounds, and suitability for industrial production.

Description

technical field [0001] The invention belongs to the technical field of pharmaceutical chemical synthesis, and in particular relates to a method for constructing a steroid-6β, 7β-methylene structure through series reactions. Background technique [0002] The steroidal-6β, 7β-methylene structure is a key intermediate in the synthesis of a new type of steroidal progestin Drospirenone (Drospirenone). The classical chemical methods for the construction of 6β, 7β-methylene structural units all use the Δ of conjugated diene compounds 6 Micheal addition to the -ene position with Corey methyleneating reagents; or Simmons-Smith addition using Zn-Cu / dihalomethane. Later, it was improved to achieve Simmons-Smith addition directed by 5β-hydroxyl orientation, and its stereoselectivity and yield were greatly improved. But the introduction of 5β-hydroxy-Δ 6 The -alkene structural unit must be obtained through group protection, allylic oxidation, selective reduction, 5β, 6β-epoxidation, h...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07J75/00C07J53/00C07J21/00
Inventor 贺诗华
Owner XIAN UNIV OF SCI & TECH
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