Use of sulfur-containing fused heterotetracyclic azasugar derivatives
A technology of tetracyclic azasaccharides and derivatives, applied in the field of anti-HIV virus drugs, can solve the problems of no relevant reports on biological activity, etc., to alleviate the trouble of drug resistance of HIV virus drug resistance, facilitate large-scale production, Effect of Good HIV Reverse Transcriptase Inhibitory Activity
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Embodiment 1
[0040] Preparation of raw material five-membered aza-urethane compound 1a((3aS,4R,6aR)-tert-butyl-2,2-dimethyl-4-formyldihydro-3aH-[1,3]dioxolane[ 4,5-c)pyrrole-5(4H)-carboxylate)
[0041] The preparation method is as follows:
[0042] (1) Synthesis of compound II-b((3aS,6R,6aS)-6-[(R)-2,2-dimethyl-1,3-dioxolane-4-yl]-2,2- Dimethyltetrahydrofuran [3,4-d][1,3]dioxolane-4-ol):
[0043] Add 20g anhydrous D-mannose (compound Ia, 0.11mol, a commercially available product) and 600mL acetone into a 1000mL round-bottom flask, add 14.0mL concentrated sulfuric acid (content 98%) while stirring, and stir at room temperature under the protection of nitrogen About 5h (TLC monitoring reaction), after the reaction is complete, add anhydrous sodium carbonate powder, neutralize the reaction solution to colorless, remove unreacted sodium carbonate by suction, wash the filter cake with a small amount of acetone (20-30mL), and reduce pressure Evaporate the acetone, add 200mL of dichloromethane to dis...
Embodiment 2
[0059] Synthesis of (4R)-tert-butyl 4-[(S)-3-(2-ethoxy-2-oxoethyl)-4-carbonyl-3,4-dihydro-2H-benzo[e] [1,3]thiazin-2-yl]-2,2-dimethyldihydro-3aH-[1,3]dioxazole [4,5-c]pyrrole-5(4H)-carboxylate (Abbreviated as compound 2a) and (4R)-tert-butyl 4-((R)-3-(2-ethoxy-2-oxoethyl)-4-carbonyl-3,4-dihydro-2H- Benzo[e][1,3]thiazin-2-yl]-2,2-dimethyldihydro-3aH-[1,3]dioxazole[4,5-c]pyrrole-5(4H )-Carboxylate (abbreviated as compound 2b)
[0060] The chemical reaction process is as follows:
[0061]
[0062] The specific method is:
[0063] In a 25mL eggplant-shaped flask, add five-membered aza-urethane 1a (127mg, 0.47mmol, 1.2 equivalent), glycine ethyl ester hydrochloride (54mg, 1 equivalent), NaHCO 3 Powder (34mg, 1 equivalent), dissolved in freshly distilled toluene, N 2 After stirring for 30 minutes under protection at 40°C, TLC monitoring showed that the reaction of five-membered aza-urethane 1a was completely added mercaptosalicylic acid (120mg, 2eq), and N,N'-dicyclohexylcarbodiimide (D...
Embodiment 3
[0067] Synthesis of (3aS, 4R, 6aR)-tert-butyl 4-{(S)-3-[(S)-1-ethoxy-1-oxopropyl-2-yl]-4-carbonyl-3, 4-Dihydro-2H-benzo[e][1,3]thiazin-2-yl}-2,2-dimethyldihydro-3aH-[1,3]dioxazole[4,5- c]pyrrole-5(4H)-carboxylate (compound 2c for short) and (3aS,4R,6aR)-tert-butyl 4-{(R)-3-[(S)-1-ethoxy-1 -Oxopropyl-2-yl]-4-carbonyl-3,4-dihydro-2H-benzo[e][1,3]thiazin-2-yl}-2,2-dimethyldi Hydrogen-3aH-[1,3]dioxazole[4,5-c]pyrrole-5(4H)-carboxylate (abbreviated as compound 2d)
[0068] The chemical reaction process is as follows:
[0069]
[0070] The specific method is:
[0071] In a 25mL eggplant-shaped flask, add five-membered aza-urethane 1a (164mg, 0.60mmol) and L-alanine methyl ester hydrochloride (93mg, 1.0 equivalent), NaHCO 3 Powder (1.2 equivalent), dissolved with freshly steamed toluene, N 2 After stirring for 1 hour under protection at 55°C, TLC monitoring showed that the reaction of compound 1a was completely added mercaptosalicylic acid (188mg, 2.0 equivalent), N,N'-dicyclohexylcarbod...
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