Benzodioxane derivatives and their pharmaceutical use
A technology of alkyl and phenyl, which is applied in the field of benzodioxane derivatives and their pharmaceutical applications, can solve the problems associated with side effects, elevated blood pressure, heart rate, gastrointestinal secretion and anxiety, etc., to improve solubility and enhance Potency, effect of improving selectivity
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[0138] Preparation of Compounds of the Disclosure
[0139] General Method A
[0140] The 1-(piperidin-3-yl) derivative (1 equiv) was dissolved in acetonitrile or DMF (~1M) in a microtube. Add DIPEA (0-1.2 equiv), K 2 CO 3 (1.5-2.5 equiv) and benzodioxene derivative (1-1.2 equiv), and seal the vial. The reaction mixture was heated at 120°C for 3 hours. The solvent was removed under reduced pressure.
[0141] General Method B
[0142] To a solution of the appropriate 4-oxobutyrate derivative (1 equiv) and (S)-3-aminopiperidine derivative (1-1.1 equiv) in DCE (0.1-0.2M) was added at 0°C NaBH(OAc) 3 (1.2-2 equivalents), then stirred at room temperature for 6-18h. The reaction mixture was quenched with water and extracted with DCM. The organic layer was dried and evaporated.
[0143] General Method C
[0144] To a solution of the appropriate 2-hydroxyacetamide (asetamide) derivative (1 equivalent) in DMF (0.1-0.28M) was added Et at 0 °C 3 N or DIPEA (2-3 eq) followed by...
Embodiment 1
[0157] Example 1: 1-((S)-1-(((S)-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methyl)piperidine-3 -yl)-4,4-dimethylpyrrolidin-2-one
[0158] Step 1: Benzyl (S)-3-(4,4-dimethyl-2-oxopyrrolidin-1-yl)piperidine-1-carboxylate
[0159] According to general method B using methyl 3,3-dimethyl-4-oxobutyrate (1.5 g, 10.4 mmol, Organic Syntheses 1993, 71, 189), benzyl (S)-3-aminopiperidine-1-carboxylate (2.68g, 11.4mmol) and NaBH(OAc) 3 (2.64g, 12.5mmol) and DCE (100ml) to prepare benzyl (S)-3-(4,4-dimethyl-2-oxopyrrolidin-1-yl)piperidine-1-carboxylate. The product was purified by flash chromatography to afford 1 g of benzyl (S)-3-(4,4-dimethyl-2-oxopyrrolidin-1-yl)piperidine-1-carboxylate.
[0160] LC-MS (ES+) [M+1]: 331.2.
[0161] Step 2: (S)-4,4-Dimethyl-1-(piperidin-3-yl)pyrrolidin-2-one
[0162] Benzyl (S)-3-(4,4-dimethyl-2-oxopyrrolidin-1-yl)piperidine-1-carboxylate (1.2 g, 3.6 mmol) from step 1 was used according to general procedure D ), 10% Pd / C (200mg) and EtOAc (50ml) to prepar...
Embodiment 2
[0167] Example 2: 1-((S)-1-(((S)-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methyl)piperidine-3 -yl)-4,4-diphenylimidazolidin-2-one
[0168] Step 1: Benzyl (2-oxo-1,1-diphenylethyl)carbamate
[0169]Benzyl (2-hydroxy-1,1-diphenylethyl)carbamate (8.0 g, 23.05 mmol, European Journal of Organic Chemistry, 2008(2), 350) was stirred ice-cold in DCM (200 ml) A mixture of PCC (9.9 g, 46.10 mmol) and silica gel (10 g) was added to the solution and stirred at room temperature for 12 h. The reaction mixture was diluted with DCM and filtered through a pad of celite. Evaporation of the filtrate gave crude compound which was purified by flash column to give 4.0 g of product.
[0170] LC-MS (ES+) [M+1]: 346.1.
[0171] Step 2: (S)-tert-butyl 3-((2-(((benzyloxy)carbonyl)amino)-2,2-diphenylethyl)amino)-piperidine-1-carboxylate
[0172] (S)-tert-butyl 3-aminopiperidine-1-carboxylate (2.32 g, 11.59 mmol), (2-oxo-1,1-diphenylethyl) from step 1 was used according to general procedure B - Benzyl ca...
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