A kind of o-alkynyl phenol ether glycosidation donor and its preparation method and application
An alkynyl phenol ether, glycosidation reaction technology, which is applied in the preparation of sugar derivatives, chemical instruments and methods, esterification of saccharides, etc. Effects of stable ortho-alkynyl phenol ether glycosylation donors and mild reaction conditions
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[0042] The preparation of the compound shown in formula II:
[0043] 1. Preparation of Compound II-1
[0044]
[0045] In the nitrogen protection reaction system, the whole Ac-protected glucose III-1 (167mg, 0.43mmol) and o-iodophenol (248mg, 1.13mmol) were dissolved in dry DCM (3mL), and Et was slowly added dropwise under an ice-water bath. 3 N (0.06mL, 0.43mmol) was stirred for 5 minutes, then slowly added BF 3 ·Et 2 O (0.27 mL, 2.14 mmol). Warm up to room temperature and react for 4.5 days. Slowly add a large amount of Et after cooling down to 0°C 3 The reaction was extracted with N, spin-dried under vacuum and then applied to the chromatography column, and passed through the column with (PE / EA / DCM=4.5:1:1) to obtain white solid compound II-1 (130mg, 55%): [α] 28 D =-55.5° (c=1.0, CHCl 3 ); 1 HNMR (400MHz, CDCl 3 )δ7.79(dd, J=1.2,7.6Hz,2H),7.32(td,J=1.6,8.4Hz,1H),7.07(dd,J=1.2,8.4Hz,1H),6.85(td,J =1.2,7.6Hz,1H),5.42(dd,J=7.6,9.2Hz,1H),5.32(t,J=9.2Hz,1H),5.22(t,...
Embodiment 1
[0073] Example 1: Preparation of Donor 1-1 by Sonogashira Reaction:
[0074]
[0075] Solid compound II-1 (1g, 1.82mmol), Ph3P (218mg, 0.82mmol), Pd(PPh3)2Cl2 (123mg, 0.18mmol), CuI (156mg, 0.82mmol) were dissolved in DMF (4mL) and iPr2NH (18mL ) in a mixed solvent, under the protection of nitrogen, the temperature was lowered to -78°C, and the gas was ventilated with a vacuum diaphragm pump. After repeating three gas exchanges, p-methoxyphenylacetylene (360 mg, 2.73 mmol) dissolved in DMF (4 mL) was added. After heating up to 70°C, the reaction was carried out for 4 hours. Spot the plate to monitor the reaction for complete addition of NH 4 The reaction was extracted with Cl, diluted with ethyl acetate, then filtered with diatomaceous earth and silica gel powder, and then saturated with NH 4 After washing three times with Cl, the combined organic phase was washed twice with saturated NaCl. with anhydrous Na 2 SO 4 dry. Pad the silica gel powder to filter, and the fi...
Embodiment 2
[0076] Example 2: Preparation of Donor 1-1 by Sonogashira Reaction:
[0077] The synthetic experimental operation refers to the synthetic steps of Example 1; the difference is: compound II-1, Ph 3 P, Pd(PPh 3 ) 2 Cl 2 , CuI and the mol ratio of p-methoxyphenylacetylene are 1:0.2:0.1:0.2:1.2; in the first organic solvent, DMF and i PR 2 The volume ratio of NH was 1:5; the concentration of compound II-1 in the first organic solvent was 0.1 mol / L, after the reaction was complete, light yellow compound I-2 was obtained with a yield of 88%.
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