Synthetic method of β-d-mannuronic acid oligosaccharide or glycoside

A technology for the synthesis of uronic acid oligosaccharides and methods, applied in the field of organic synthesis, can solve the problems of harsh reaction conditions, difficult control, cumbersome operation, etc., and achieve the effects of high reaction yield, simple operation, and good stereoselectivity

Active Publication Date: 2016-08-10
OCEAN UNIV OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The D-mannuronic acid thioside donor developed by the van der Marel group is currently the most effective direct method to construct its β-glycosidic bond (J.Am.Chem.Soc.2006,128,13066), but this method requires The equivalent accelerator preactivates the donor, the reaction conditions are harsh and the operation is cumbersome, and it is not easy to control

Method used

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  • Synthetic method of β-d-mannuronic acid oligosaccharide or glycoside
  • Synthetic method of β-d-mannuronic acid oligosaccharide or glycoside
  • Synthetic method of β-d-mannuronic acid oligosaccharide or glycoside

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-9

[0031] Embodiment 1-9: the synthesis of compound 3a, 3b, 3c, 3e, 3f, 3g, 3i, 3j, 3k

[0032] Under argon protection, add fresh activated AW-300 or Molecular sieves (3g / mmol), D-mannuronic acid o-alkynyl benzoate 1 (1.2-1.5mol), monosaccharides or alcohols or phenols 2a, 2b, 2c, 2e, 2f, 2g, 2i, 2j, One of 2k (1.0mol) and AgB (C 6 f 5 ) 4 (0.1mol), followed by injection of freshly distilled anhydrous CH 2 Cl 2 (2mL), after stirring at 0°C for 30min, add (4-MeOPh) 3 PAuCl (0.1mol) and AgB (C 6 f 5 ) 4 (0.1mol), continue to stir for 0.5-24 hours after TLC detects that the reaction is complete. The reaction was quenched with triethylamine and filtered, the filtrate was concentrated under reduced pressure, and column chromatography gave compounds 3a, 3b, 3c, 3e, 3f, 3g, 3i, 3j, 3k, respectively.

Embodiment 10-12

[0033] Embodiment 10-12: the synthesis of compound 3h, 3l, 3n

[0034] Similar to the steps of Example 1-9, with Ph 3 PAuCl (0.1mol) and AgB (C 6 f 5 )4 (0.1mol) as accelerator, D-mannuronic acid o-alkynyl benzoate 1 reacts with steroidal saponin 2h, 2l, 2n respectively to obtain 3h, 3l, 3n.

Embodiment 13-15

[0035] Embodiment 13-15: the synthesis of compound 3d, 3m, 3o

[0036] Similar to the steps of Example 1-9, with Me 3 PAuCl (0.1mol) and AgB (C 6 f 5 ) 4 (0.1mol) as accelerator, D-mannuronic acid o-alkynyl benzoate 1 reacts with one of triterpenoid saponin 2d, 2m, and triterpenoid saponin 2o respectively to obtain 3d, 3m, and 3o.

[0037] The data for compounds 3a-3o are as follows:

[0038] Compound 3a data:

[0039] Yield: 85%;

[0040] [α] D 20 -134.0 (c2.33, CHCl 3 );

[0041] 1 H NMR (600MHz, CDCl 3 )δ7.43(d,J=6.6Hz,2H),7.37(d,J=7.7Hz,2H),7.35-7.29(m,6H),7.26(m,4H),7.14(d,J=8.3 Hz,2H),5.65(s,1H),5.50(t,J=9.9Hz,1H),4.93(d,J=13.2Hz,2H),4.80(d,J=12.1Hz,1H),4.50( d,J=12.7Hz,1H),4.38(d,J=12.1Hz,1H),4.30(d,J=5.5Hz,1H),4.17-4.11(m,2H),3.94(d,J=2.8 Hz,1H),3.79(d,J=9.8Hz,1H),3.75(dd,J=9.9,7.7Hz,1H),3.70(s,3H),3.51(dd,J=9.9,3.3Hz,1H ),2.71(t,J=7.1Hz,2H),2.54(td,J=6.7,4.5Hz,2H),2.34(s,3H),2.16(s,3H),1.47(s,3H),1.34 (s,3H),1.30(d,J=6.2Hz,3H);

[0042] 13 C NMR (150...

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Abstract

The invention relates to a method for synthesizing beta-oligosaccharide or glucoside 3 stereoselectively by D-mannuronic acid o-alkynyl benzoate 1, wherein R1-R5 adopts one of C1-C6 alkyl, C3-C6 naphthenic base, silicon substrate and acyl-substituted methyl; and R6OH adopts one of acyl, silicon substrate or alkyl protected monohydroxy or polyhydroxy-sugar, simple alcohol or phenol, steroid sapogenin, steroid saponin, triterpenoid sapogenin or triterpenoid saponin. The synthetic method has the advantages as follows: (1) catalytic amount of an organic gold compound is used as an accelerator for a reaction; (2) the reaction conditions are mild (0-30 DEG C), and the operation is simple and convenient; and (3) the reaction yield is high, and the stereoselectivity is good.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method for stereoselectively synthesizing beta-oligosaccharides or glycosides of D-mannuronic acid o-alkynyl benzoate. technical background [0002] Natural products containing β-mannuronic acid units widely exist in extremely important biological activities. β-D-mannuronic acid oligosaccharides not only have the effects of promoting plant root growth, inhibiting bacteria, and promoting the growth of human keratinocytes, but also can combine with Toll-like receptors 2 and 4 to display immune regulation. Sulfated mannuronic acid oligosaccharides derived from alginate JG 3 Not only can it act as a heparanase inhibitor, inhibit tumor angiogenesis and metastasis in vitro and in vivo (Cancer Res.2006,66,8779-8787), but also bind to tubulin to stop cancer cells in G 2 / M stage, leading to its apoptosis, thereby inhibiting the growth of tumor cells. Therefore, JG 3 It may be used as...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07H9/04C07H1/00C07J63/00C07H15/02C07J9/00C07H15/256
Inventor 李明王鹏
Owner OCEAN UNIV OF CHINA
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