Ethyl Acetate → Tert-butyl 6-(6-aminopyridin-3-yl)-2,6-diazaspiro[3.3]heptane-2-carboxylate

HRID 1431087Notes

Reaction equation

[N+:1]([C:4]1[N:9]=[CH:8][C:7]([N:10]2[CH2:23][C:12]3([CH2:15][N:14]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:13]3)[CH2:11]2)=[CH:6][CH:5]=1)([O-])=O.C(OCC)(=O)C>[Pd].CO>[C:19]([O:18][C:16]([N:14]1[CH2:13][C:12]2([CH2:23][N:10]([C:7]3[CH:8]=[N:9][C:4]([NH2:1])=[CH:5][CH:6]=3)[CH2:11]2)[CH2:15]1)=[O:17])([CH3:22])([CH3:20])[CH3:21]

Participants

Conditions

Temperature: 25 °C

Procedure

In a 500 mL pear-shaped flask, tert-butyl 6-(6-nitropyridin-3-yl)-2,6-diazaspiro[3.3]heptane-2-carboxylate (4.54 g, 14.2 mmol) and 10% Pd/C (662 mg, 6.22 mmol) were combined with ethyl acetate (150 ml) and methanol (50 ml) to give a black suspension. The mixture was evacuated and filled with H2 twice, then stirred overnight at 25° C. under balloon pressure of H2. The mixture was filtered over celite and the filter cake was washed with MeOH. The filtrate was concentrated in vacuo to give a purple oily solid. The crude material was purified by flash chromatography (silica gel, 12 g, 0% to 4% MeOH in DCM) to afford 1.29 g (31%) of the title compound as an impure dark red solid. (M+H)+=291 m/e.

Workup

customto give a black suspension
customThe mixture was evacuated
additionfilled with H2 twice
filtrationThe mixture was filtered over celite
washthe filter cake was washed with MeOH
concentrationThe filtrate was concentrated in vacuo
customto give a purple oily solid
customThe crude material was purified by flash chromatography (silica gel, 12 g, 0% to 4% MeOH in DCM)

Sources & evidence

ORD record: ord-503b1ab7b4f24188805281c369fb4625
Source dataset: uspto-grants-2015_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08940741B2

Reaction notes

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