Oseltamivir amino derivative as well as preparation method and application thereof
A technology of Wei amino and derivatives, applied in the fields of organic synthesis and medical applications, can solve the problems of inconvenient administration, invisible, low bioavailability and the like
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Embodiment 1
[0037] Example 1: Target compound (3R,4R,5S)-4-acetamido-3-(pentane-3-oxyl)-5-((2-chloro-4-(2-thiophene)benzyl) Preparation of amino)cyclohexane-1-enecarboxylic acid (9a)
[0038]
[0039] 2-thiophene boronic acid (1) (0.64g, 5.0mmol), 4-bromo-2-chlorobenzaldehyde (3a) (1.09g, 5.0mmol, 1.0equiv), K 2 CO 3 (3.1g, 22.5mmol, 4.5equiv.) and Pd(PPh 3 ) 4 (0.064g, 0.055mmol, 0.011equiv.) was dissolved in 20mL of DMSO, with N 2 Protection, vacuuming 2-3 times, reflux for 10h. TLC detects that after the reaction is completed, 150 mL of water is added to the reaction solution, extracted with ethyl acetate (50 mL×3), the combined organic phase is washed with saturated sodium chloride solution, the organic phase is retained and dried with anhydrous magnesium sulfate, filtered, and the filtrate Concentrated under reduced pressure, the resulting crude product was separated and purified by silica gel column chromatography (developing solvent: ethyl acetate:petroleum ether=1:50 syste...
Embodiment 2
[0045] Example 2: Target compound (3R,4R,5S)-4-acetamido-3-(pentane-3-oxyl)-5-((2-chloro-4-(3-thiophene)benzyl) Preparation of amino)cyclohexane-1-enecarboxylic acid (10a)
[0046]
[0047] The preparation of compound 10a, the operation steps are the same as in Example 1, the difference is that the raw material for preparing compound 5a in Example 1 is replaced by 3-thiophene boronic acid to prepare 6a, and after obtaining 6a, follow the same steps to prepare 8a, and after obtaining 8a 10a was prepared following the same procedure.
[0048] White powdery solid, total yield 67.3%, mp: 160-162°C.
[0049] Spectral data:
[0050] 1 H NMR (400MHz, CD 3 OD)δ7.83(d,J=1.5Hz,1H),7.78(d,J=1.5Hz,1H),7.70(dd,J=8.0,1.6Hz,1H),7.61–7.42(m,3H) ,6.86(s,1H),4.34(d,J=15.7Hz,2H),4.22(d,J=7.8Hz,1H),4.11(d,J=10.7Hz,1H),3.59–3.39(m, 3H), 3.12–2.96(m, 1H), 2.61(dd, J=17.6, 9.8Hz, 1H), 2.05(s, 3H), 1.53(dd, J=11.9, 6.1Hz, 4H), 0.91(dt ,J=10.2,7.4Hz,6H).C 25 h 31 ClN 2 o 4 S, ESI-MS: m / z...
Embodiment 3
[0051] Example 3: Target compound (3R,4R,5S)-4-acetamido-3-(pentane-3-oxyl)-5-((5-chloro-4-(2-thiophene)benzyl) Preparation of amino)cyclohexane-1-enecarboxylic acid (9b)
[0052]
[0053] The preparation of compound 9b, the operation steps are the same as in Example 1, the difference is that the raw material for preparing compound 5a in Example 1 is replaced by 4-bromo-3-chlorobenzaldehyde to prepare 5b, and after obtaining 5b, follow the same steps to prepare 7b , to obtain 7b and then follow the same procedure to prepare 9b.
[0054] White powdery solid, total yield 77%, mp: 166-169°C.
[0055] Spectral data:
[0056] 1 H NMR (400MHz, CD 3 OD)δ7.80–7.61(m,2H),7.54(dd,J=5.1,1.0Hz,1H),7.47–7.38(m,2H),7.14(dd,J=5.1,3.7Hz,1H), 6.86(s,1H),4.37(d,J=13.3Hz,1H),4.25–4.06(m,3H),3.62–3.38(m,3H),3.13–2.91(m,1H),2.61(dd, J=17.3,9.7Hz,1H),2.04(d,J=7.0Hz,3H),1.54(dt,J=11.5,5.8Hz,4H),0.91(q,J=7.5Hz,6H).C 25 h 31 ClN 2 o 4 S, ESI-MS: m / z 491.00[M+H] + .
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