Triacetoxyperiodinane → Methyl 2-(2-bromo-7-(4,4-dimethylpiperidin-1-yl)-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-oxoacetate

HRID 574353Notes

Reaction equation

HRID 574353 reaction equation
[Br:1][C:2]1[CH:25]=[C:5]2[N:6]=[C:7]([CH3:24])[C:8]([CH:18]([OH:23])[C:19]([O:21][CH3:22])=[O:20])=[C:9]([N:10]3[CH2:15][CH2:14][C:13]([CH3:17])([CH3:16])[CH2:12][CH2:11]3)[N:4]2[N:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[Br:1][C:2]1[CH:25]=[C:5]2[N:6]=[C:7]([CH3:24])[C:8]([C:18](=[O:23])[C:19]([O:21][CH3:22])=[O:20])=[C:9]([N:10]3[CH2:15][CH2:14][C:13]([CH3:17])([CH3:16])[CH2:12][CH2:11]3)[N:4]2[N:3]=1

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 86695078Methyl 2-(2-bromo-7-(4,4-dimethylpiperidin-1-yl)-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-hydroxyacetate

Product 1

HCID 86695079Methyl 2-(2-bromo-7-(4,4-dimethylpiperidin-1-yl)-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-oxoacetateYield 56%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of methyl 2-(2-bromo-7-(4,4-dimethylpiperidin-1-yl)-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-hydroxyacetate (1.28 g, 3.11 mmol, 1 equiv) in DCM (16 mL) was added Dess-Martin periodindane (1.85 g, 4.36 mmol, 1.4 equiv). After 30 min, the reaction was added saturated aqueous NHCO3 and extracted with DCM (×3). The combined DCM extracts were dried over Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel flash chromatography (0-50% EtOAc/hexane) to provide methyl 2-(2-bromo-7-(4,4-dimethylpiperidin-1-yl)-5-methylpyrazolo[1,5-a]pyrimidin-6-yl)-2-oxoacetate as a yellow solid (0.71 g, 56%). 1H NMR (400 MHz, CDCl3) δ 6.56 (s, 1H), 3.94 (s, 3H), 3.58-3.43 (m, 4H), 2.55 (s, 3H), 1.64-1.50 (m, 4H), 1.05 (s, 6H); LCMS (ESI, M+1): 409.2.

Workup

  1. extractionextracted with DCM (×3)
  2. dry with materialThe combined DCM extracts were dried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by silica gel flash chromatography (0-50% EtOAc/hexane)

Sources & evidence

ORD record
ord-072385ccbac9416fbd98ff3e8b54ef26
Source dataset
uspto-grants-2015_05
Patent number
US09034882B2

Reaction notes

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