Sodium Iodide → tert-Butyl 4-(acetylthio)piperidine-1-carboxylate

HRID 1802388Notes

Reaction equation

[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11](Br)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:15]([O-:18])(=[S:17])[CH3:16].[K+].[Na+].[I-]>CN(C=O)C>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([S:17][C:15](=[O:18])[CH3:16])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 50 °C

Procedure

To a solution of 6.9 g (0.02 mol) of 4-bromo-piperidine-1-carboxylic acid tert-butyl ester in DMF (18 mL) are added 5.25 g (0.012 mmol) potassium thioacetate, followed by a catalytic amount of NaI (0.35 g, 10 mol %) at room temperature. After complete addition, the reaction is heated to 50° C. for 20 h. The reaction mixture is partitioned between ethyl acetate (100 mL) and water (100 mL). The organic layer is dried over Na2SO4, filtered and the solvent is removed under reduced pressure to afford 5.41 g of 4-acetylsulfanyl-piperidine-1-carboxylic acid tert-butyl ester as a brown oil. Yield: 81%; ES-MS: m/z 245 [M+H—CH3], 160 [M+H—O5H9O2]; 1H NMR (250 MHz, CHLOROFORM-d) δ ppm 1.37-1.64 (11 H, m), 1.78-1.99 (2 H, m), 2.25-2.35 (3 H, m), 3.06 (2 H, ddd, J=13.63, 10.43, 3.05 Hz), 3.61 (1 H, tt, J=10.28, 4.04 Hz), 3.76-3.96 (2 H, m)

Workup

additionAfter complete addition
customThe reaction mixture is partitioned between ethyl acetate (100 mL) and water (100 mL)
dry with materialThe organic layer is dried over Na2SO4
filtrationfiltered
customthe solvent is removed under reduced pressure

Sources & evidence

ORD record: ord-ec098b75cf6b49a8a4c86f5cc5734a00
Source dataset: uspto-grants-2013_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08349871B2

Reaction notes

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