2-aza-bicyclo[2.2.1]heptane compounds and uses thereof
A compound, the technology of heterocycloalkyl, applied in the field of 2-aza-bicyclo[2.2.1]heptane compounds, can solve problems such as neurotoxicity
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Embodiment 1
[0271] Example 1. (R * ) -N-(7-Azabicyclo[2.2.1]heptan-1-yl(phenyl)methyl)-2,6-dimethylbenzamide.
[0272]
[0273] Step A. Preparation of 7-azabicyclo[2.2.1]heptane-1,7- from (1s, 4s)-7-azabicyclo[2.2.1]heptane-1-carboxylic acid hydrochloride Dicarboxylic acid·7-tert-butyl ester·1-methyl ester.
[0274]
[0275] Acetyl chloride (3.90 mL, 54.89 mmol) was slowly added to methanol (80 mL) at 0°C. After 10 minutes, the solution was added to (1s, 4s)-7-azabicyclo[2.2.1]heptane-1-carboxylic acid (3.25 g, 1830 mmol; according to A. Avenoza et al. Tetrahedron 2001, 57, 545-548) to obtain a beige mixture. The mixture was warmed to 60°C and maintained under these conditions for 16 hours. The mixture was concentrated to a minimum volume, concentrated again from methanol, and dried under vacuum to give crude (1s, 4s)-7-azabicyclo[2.2.1]heptane-1-carboxylic acid methyl ester (3.46g) , It is hydrochloride and light gray solid. To crude 7-azabicyclo[2.2.1]heptane-1-carboxylic acid methyl es...
Embodiment 2
[0300] Example 2. Preparation (R * )-N-((7-Methyl-7-azabicyclo[2.2.1]heptan-1-yl)(phenyl)methyl)-2-(methylthio)nicotinamide
[0301]
[0302] Step A. From (R * )-1-(Amino(phenyl)methyl)-7-azabicyclo[2.2.1]heptane-7-carboxylic acid tert-butyl ester preparation (R * )-1-((Benzyloxycarbonylamino)(phenyl)methyl)-7-azabicyclo[2.2.1]heptane-7-carboxylic acid tert-butyl ester
[0303]
[0304] To (R * )-1-(Amino(phenyl)methyl)-7-azabicyclo[2.2.1]heptane-7-carboxylic acid tert-butyl ester (0.133g, 0.44mmol; according to step AF of Example 1 Operational preparation) and DIPEA (0.230 mL, 1.32 mmol) in dichloromethane (4.09 mL) was added benzyl chloroformate (0.073 mL, 0.48 mmol). The resulting light yellow solution was stirred for 20 minutes and another 35 uL of benzyl chloroformate was added. The reaction was stirred for another 45 minutes, then quenched with methanol (1 mL) and concentrated to a minimum volume. The resulting solution was passed through flash column chromatography (SiO 2 ...
Embodiment 32
[0317] Example 3.2 Preparation of 6-Dimethyl-N-((7-methyl-7-azabicyclo[2.2.1]heptan-1-yl)(phenyl)methyl)benzamide
[0318]
[0319] Step A. Preparation of 7-formyl-7-azabicyclo[2.2.1] from (1s, 4s)-7-azabicyclo[2.2.1]heptane-1-carboxylic acid methyl ester hydrochloride Methyl heptane-1-carboxylate
[0320]
[0321] At 0°C, to acetic anhydride (1.596 mL, 16.92 mmol) was added formic acid (0.757 mL, 17.63 mmol). After 5 minutes, the clear, colorless solution was warmed to 60°C. After 1 hour, the solution was cooled, and 0.5 mL was added to triethylamine (9.83 mL, 70.50 mmol) and (1s, 4s)-7-azabicyclo[2.2.1]heptane-1 at 0°C -A mixture of methyl carboxylate hydrochloride (2.70 g, 14.1 mmol; prepared according to the procedure of A. Avenoza et al. Tetrahedron 2001, 57, 545-548) in dichloromethane (70 mL). After 10 minutes, the white mixture was diluted with saturated aqueous sodium bicarbonate and extracted with ethyl acetate (x3). The combined organic layer was dried over sodium su...
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