m-Chloroperbenzoic acid → tert-butyl(3S)-3-[4-(2-aminopyrimidin-5-yl)-2-(methylsulfinyl)-5,6-dihydro-7H-pyrrolo[2,3-d]pyrimidin-7-yl]-3-methylpyrrolidine-1-carboxylate

HRID 1775494Notes

Reaction equation

HRID 1775494 reaction equation
[NH2:1][C:2]1[N:7]=[CH:6][C:5]([C:8]2[C:9]3[CH2:18][CH2:17][N:16]([C@@:19]4([CH3:31])[CH2:23][CH2:22][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:20]4)[C:10]=3[N:11]=[C:12]([S:14][CH3:15])[N:13]=2)=[CH:4][N:3]=1.ClC1C=C(C=CC=1)C(OO)=[O:37]>C(Cl)Cl.CS(C)=O>[NH2:1][C:2]1[N:7]=[CH:6][C:5]([C:8]2[C:9]3[CH2:18][CH2:17][N:16]([C@@:19]4([CH3:31])[CH2:23][CH2:22][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:20]4)[C:10]=3[N:11]=[C:12]([S:14]([CH3:15])=[O:37])[N:13]=2)=[CH:4][N:3]=1

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 118436590tert-butyl(3S)-3-[4-(2-aminopyrimidin-5-yl)-2-(methylsulfanyl)-5,6-dihydro-7H-pyrrolo[2,3-d]pyrimidin-7-yl]-3-methylpyrrolidine-1-carboxylate

Product 1

HCID 118436079tert-butyl(3S)-3-[4-(2-aminopyrimidin-5-yl)-2-(methylsulfinyl)-5,6-dihydro-7H-pyrrolo[2,3-d]pyrimidin-7-yl]-3-methylpyrrolidine-1-carboxylateYield 55%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of tert-butyl(3S)-3-[4-(2-aminopyrimidin-5-yl)-2-(methylsulfanyl)-5,6-dihydro-7H-pyrrolo[2,3-d]pyrimidin-7-yl]-3-methylpyrrolidine-1-carboxylate (352 mg, 0.794 mmol) in DCM (8 mL) was added m-chloroperoxybenzoic acid (254 mg, 1.03 mmol, 70% purity) in three portions over 1 min at 0° C. The reaction mixture was stirred at 0° C. for 30 min. Four drops of DMSO was added and the reaction mixture was stirred for 5 min. The reaction mixture was purified via HPLC reversed phase column (XBridge C18 30×250 mm, mobile phase: 0%-50% of water with 0.1% EtOAc to acetonitrile with 0.1% EtOAc over 30 min, flow rate 80 mL/min) to give the title compound (200 mg, 55%) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ 8.78 (s, 2 H), 7.18 (s, 2 H), 3.89-3.75 (m, 2 H), 3.73-3.62 (m, 3 H), 3.42-3.34 (m, 3 H), 2.82 (s, 3 H), 2.41 (br s, 1 H), 2.15-2.01 (m, 1 H), 1.41 (s, 9 H), 1.33 (s, 3 H). m/z (APCI+) for C21H29N7O3S 460.6 (M+H)+.

Workup

  1. stirringthe reaction mixture was stirred for 5 min
  2. customThe reaction mixture was purified via HPLC
  3. customphase column (XBridge C18 30×250 mm, mobile phase: 0%-50% of water with 0.1% EtOAc to acetonitrile with 0.1% EtOAc over 30 min, flow rate 80 mL/min)

Sources & evidence

ORD record
ord-7cfd7b8b69dc488885312af0c1574e29
Source dataset
uspto-grants-2016_02
Patent number
US09260439B2

Reaction notes

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