Fused cyclic gamma-amino acid derivative, preparation method of fused cyclic gamma-amino acid derivative, and application of fused cyclic gamma-amino acid derivative to pharmaceuticals
A compound and cycloalkyl technology, applied in the field of fused-ring γ-amino acid derivatives, can solve the problems of low safety, dependence, and patients with abuse
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Embodiment 1
[0117] Example 1: (±)-2-((1R,5R,6S)-6-(aminomethyl)spiro[bicyclo[3.2.0]heptane-3,1'-cyclopropane]-6-yl) Acetic acid (compound 1)
[0118] (±)-2-((1R,5R,6S)-6-(aminomethyl)spiro[bicyclo[3.2.0]heptane-3,1'-cyclo propan]-6-yl)acetic acid
[0119]
[0120] The first step: (±)-2-((1S,5R)-bicyclo[3.2.0]hept-2-en-6-ylidene)ethyl acetate (1B)
[0121] (±)-ethyl 2-((1S,5R)-bicyclo[3.2.0]hept-2-en-6-ylidene)acetate
[0122] Sodium hydride (60%, 2.2g, 55.5mmol) and tetrahydrofuran (40mL) were added into the reaction flask, the temperature was lowered to 0°C, and a tetrahydrofuran solution (5mL ), dropwise, and keep warm for 1 hour, add dropwise a tetrahydrofuran solution (5mL) of bicyclo[3.2.0]hept-2-en-6-one (1A) (5g, 46.2mmol), dropwise, rise to room temperature for reaction 2 hours. Add water (50mL) and ethyl acetate (50mL) to the reaction solution, stir and separate the liquids, extract the aqueous phase with ethyl acetate (30mL×2), combine the organic phases, dry over anhydro...
Embodiment 2
[0208] Example 2: (±)-2-((1R,5R,6S)-6-(aminomethyl)spiro[bicyclo[3.2.0]heptane-3,1'-cyclobutane]-6-yl ) acetic acid (compound 2)
[0209] (±)-2-((1R,5R,6S)-6-(aminomethyl)spiro[bicyclo[3.2.0]heptane-3,1'-cyclobutan]-6-yl)acetic acid
[0210]
[0211] The first step: (±)-(1R,2S,3S,5R)-2-bromospiro[bicyclo[3.2.0]heptane-6,2'-[1,3]dioxolane]-3- Alcohol (2B)
[0212] (±)-(1R,2S,3S,5R)-2-bromospiro[bicyclo[3.2.0]heptane-6,2'-[1,3]dioxolan]-3-ol
[0213] Add (±)-(1S,5R)-spiro[bicyclo[3.2.0]hept[2]ene-6,2'-[1,3]dioxolane](2A) (9.0g , 59.14mmol), add acetone (90mL) and water (45mL) to dissolve, add N-bromosuccinimide (12.63g, 70.96mmol) under stirring at room temperature, and continue stirring at room temperature for 5 hours. Concentrate to dryness under reduced pressure, add ethyl acetate (100 mL) and water (100 mL), stir and separate the layers, extract the aqueous phase with ethyl acetate (100 mL×2), combine the organic phases, wash with saturated brine (150 mL×1), The orga...
Embodiment 3
[0270] Example 3: (±)-2-((1R,5R,6S)-6-(aminomethyl)spiro[bicyclo[3.2.0]heptane-2,1'-cyclopropane]-6-yl) Acetic acid (compound 3)
[0271] (±)-2-((1R,5R,6S)-6-(aminomethyl)spiro[bicyclo[3.2.0]heptane-2,1'-cyclopropan]-6-yl)acetic acid
[0272]
[0273] The first step: (±)-(1'R,2'S,4'R,6'R)-3'-oxaspiro[[1,3]dioxolane-2,7'-tricyclo[4.2 .0.0 2,4 ]octane](3A)
[0274] (±)-(1'R,2'S,4'R,6'R)-3'-oxaspiro[[1,3]dioxolane-2,7'-tricyclo[4.2.0.02,4]octane]
[0275] Add (±)-(1S,5R)-spiro[bicyclo[3.2.0]hept[2]ene-6,2'-[1,3]dioxolane](2A)(2.7 g, 18.0mmol) and dichloromethane (50mL), m-chloroperoxybenzoic acid (6.2g, 36.0mmol) was added in portions at room temperature, and reacted at room temperature for 2 hours. Add dichloromethane (100mL) and 2M aqueous sodium thiosulfate (100mL) to the reaction solution, stir for 30 minutes, separate the layers, extract the aqueous phase with dichloromethane (50mL×2), combine the organic phases, and wash with 2M hydrogen Wash with sodium oxide solu...
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