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Process for synthesizing pennosapogenin by 17-hydroxy-steroid internal ester

A saponin and steroid technology, applied in the direction of steroids, chemical instruments and methods, steroid preparation, etc., can solve the problems of exacerbating the shortage of plant resources, affecting the ecological environment, and destroying vegetation

Inactive Publication Date: 2006-06-28
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Since the annual consumption far exceeds the annual growth of Zhonglou, long-term excavation of wild plants not only aggravates the shortage of plant resources for many famous Chinese medicines, but also inevitably leads to vegetation destruction and affects the ecological environment

Method used

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  • Process for synthesizing pennosapogenin by 17-hydroxy-steroid internal ester
  • Process for synthesizing pennosapogenin by 17-hydroxy-steroid internal ester
  • Process for synthesizing pennosapogenin by 17-hydroxy-steroid internal ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 2

[0034] Example 2 Synthesis of Compound 2h

[0035]

[0036] 5.0 equivalents of lithium reagent was dropped into the 5mL anhydrous THF solution of 150mg of internal steroid ester 1b, reacted at -20℃ until 1a no longer decreased, and saturated NH was added 4 The Cl solution terminates the reaction. Ethyl acetate extraction (40×2mL), the ester layer was saturated with NH 4 Cl solution wash, after anhydrous Na 2 SO 4 After drying, it was concentrated under reduced pressure. The obtained crude product was separated by flash column chromatography to obtain furostane compound 3,17,20R-furostatriol 2h 43mg (21% yield), and the recovered raw material 1b 108mg (72% yield).

[0037] Compound 2h:

[0038] 1 H-NMR(300MHz, CDCl 3 ): 5.57 (d, 1H, J = 8.7 Hz, H-6), 5.51 (s, 2H, MOM), 4.17 (dd, 1H, J = 4.5, 7.5 Hz, H-16), 3.54 (m, 1H , H-3), 3.27 (s, 3H, MOM), 2.21 (q, 1H, J = 7.5 Hz, H-20), 1.46 (t, J = 8.1 Hz, 2H, H-22), 1.04 (s , 3H, H-19), 0.94 (d, 3H, J=7.2 Hz, H-21), 0....

Embodiment 3

[0040] Example 3 Compound 2a removes silicon protecting group

[0041]

[0042] 31 mg (0.043 mmol) of furostane compound 2a was dissolved in 2 mL of anhydrous THF, and 0.43 mL (0.43 mmol) of 1M TBAF in THF was injected, the temperature was raised to -60°C, the reaction was stirred, and TLC tracked until the reaction was complete. Cool to room temperature, add 10 mL of water, extract with ethyl acetate (15×3 mL), and use saturated NaHCO for the ester layer 3 Wash with NaCl solution, after anhydrous Na 2 SO 4 After drying, it was concentrated under reduced pressure. The obtained crude product is separated by flash column chromatography to obtain furostanes desiliconized product: oily 3,5-cyclo-6-methoxy-26-tert-butyldiphenylsiloxy-17,20R- Furostediol (25R)-3,5-cyclo-6-methoxy-17,22R,26-furostetriol 2f 9mg (45.2% yield) and spirostane auto-ring closure product: oily (25R )-3,5-cyclo-6-methoxy-17-spirosterol 2g 10mg (52.4% yield).

[0043] Compound 2f:

[0044] 1 H...

Embodiment 4

[0047] Example 4 Synthesis of Pennogenin (Method 1: Synthesis from Compound 2g)

[0048]

[0049] 8 mg (0.018 mmol) of 2 g of spirostane compounds were dissolved in 0.9 mL of dioxane, and then 0.1 mL of water and 2 mg of p-toluenesulfonic acid were added, the temperature was raised to reflux, and TLC followed the reaction to completion. Cool to room temperature, add saturated NaHCO 3 The solution was 5mL, extracted with ethyl acetate (10×3mL), and the ester layer was saturated with NaHCO 3 And NH 4 Cl solution wash, after anhydrous Na 2 SO 4 After drying and concentrating under reduced pressure, the crude product obtained was separated by flash column chromatography to obtain 6 mg of powdered sapogenin (77.5% yield).

[0050] Pennogenin:

[0051] 1 H-NMR(300MHz, CDCl 3 ): 5.35 (d, 1H, J = 4.2 Hz, H-6), 3.98 (dd,'t'like, 1H, J = 7.6 Hz, H-16), 3.51 (dd, 1H, J = 3.6, 10.8 Hz, H-26), 3.38 (dd,'t'like, 1H, J = 10.8 Hz, H-26), 2.04 (q, 1H, J = 7.2 Hz, H-20), 1.03 (s, 3H, H...

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Abstract

The invention relates to a method to form spraying brain sapogenin by 17-hydroxy-steroid lactone. The key process includes inducing side chain, and closing of steroid E / F loop. R1, R4 and R5 are H, MOM, Me, Et, Bn, THP, Ac, Ms, Ts, Bz, Piv, TMS, TES, TBS or TPS. R2 is OH, OMe, OEt, OMOM or OTMS. R3 is OH, OMe, OEt, OMOM, OTMS or ether linkage of R3 and R4. The invention is easy to operate, and the raw material is easy to gain.

Description

Technical field [0001] The present invention relates to a method for synthesizing Pennogenin from 17-hydroxysteroid internal esters. The cheap and easily available Diosgenin was degraded by F ring, and the 17-position hydroxyl group was introduced, and the side chain was modified to obtain 17α,22-dihydroxyfursterol. Such compounds can be used in the synthesis of sapogenin. The glycoside compound of sapogenin is one of the active ingredients of medicinal plants-the plant of the genus Aralia. The present invention provides a practical way for the chemical synthesis of sapogenin and its glycoside compounds. Background technique [0002] [0003] The glycoside compound of Pennogenin, which has a 17-hydroxy steroid spiro ring structure, is one of the active ingredients of the medicinal plant, the genus Aralia. The saponins are mainly found in the genus Araliaceae of the Trillium family. There are 24 species of this genus in the world. There are 19 species in China. They are mainly p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07J71/00C07J75/00
Inventor 田伟生朱伟明许启海王真
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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