Hydrogen Peroxide → 2-Chloro-7-(2,3-dihydroxy-propyl)-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one

HRID 1022459Notes

Reaction equation

C([N:4]1[C:8]2[N:9]=[C:10]([Cl:14])[NH:11][C:12](=[O:13])[C:7]=2[CH:6]=[CH:5]1)C=C.C[N+]1([O-])CC[O:19]CC1.OO.[C:25]([OH:29])(C)([CH3:27])[CH3:26]>O.CO.O.O.[O-][Os]([O-])(=O)=O.[K+].[K+]>[Cl:14][C:10]1[NH:11][C:12](=[O:13])[C:7]2[CH:6]=[CH:5][N:4]([CH2:26][CH:25]([OH:29])[CH2:27][OH:19])[C:8]=2[N:9]=1

Participants

Conditions

Temperature: 0 °C

Procedure

A mixture of 7-allyl-2-chloro-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one (Intermediate E, 40.8 mg, 195 μmol), 4-methylmorpholine N-oxide (11.4 mg, 97.3 μmol), and potassium osmate(VI) dihydrate (717 μg, 1.95 μmol) in tert-butanol (730 μL) and water (243 μL) cooled to 0° C. was treated with a 50% aqueous hydrogen peroxide solution (20 μL, 292 μmol). The reaction was allowed to warm to room temperature, where it stirred overnight. At this time, the reaction was diluted with methanol and absorbed onto Celite®. Flash chromatography (4 g silica gel column, 2-8% methanol/methylene chloride) afforded 2-chloro-7-(2,3-dihydroxy-propyl)-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one as an off-white solid (16.4 mg, 34.6%). 1H NMR (300 MHz, DMSO-d6) δ ppm 3.57 (s, 1H) 3.80 (d, J=9.42 Hz, 1H) 3.85-3.99 (m, 1H) 4.14-4.29 (m, 1H) 4.75 (t, J=5.75 Hz, 1H) 4.98 (d, J=5.46 Hz, 1H) 6.46 (d, J=3.39 Hz, 1H) 7.12 (d, J=3.20 Hz, 1H) 12.80 (s, 1H). LC-MS calcd. for C9H11ClN3O3 [(M+H)+] 244, obsd. 243.9.

Workup

temperatureto warm to room temperature
customabsorbed onto Celite®

Sources & evidence

ORD record: ord-70740b4f151d458e8dbe787050c9a3db
Source dataset: uspto-grants-2014_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08722661B2

Reaction notes

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