2,2-Dimethoxypropane → Tert-butyl 6'-bromo-2,2-dimethyl-2'-oxospiro[[1,3]dioxane-5,3'-indoline]-1'-carboxylate

HRID 1618790Notes

Reaction equation

HRID 1618790 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6]([CH2:21][OH:22])([CH2:19][OH:20])[C:7](=[O:18])[N:8]2[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[CH:4][CH:3]=1.O.[CH3:24][C:25]1C=CC(S(O)(=O)=O)=C[CH:26]=1.COC(OC)(C)C.C([O-])(O)=O.[Na+]>CN(C=O)C>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6]3([CH2:19][O:20][C:25]([CH3:26])([CH3:24])[O:22][CH2:21]3)[C:7](=[O:18])[N:8]2[C:11]([O:13][C:14]([CH3:16])([CH3:17])[CH3:15])=[O:12])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 64952,2-Dimethoxypropane2×HCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrate2×HCID 58221668Tert-butyl 6-bromo-3,3-bis(hydroxymethyl)-2-oxoindoline-1-carboxylate

Product 1

HCID 67285944Tert-butyl 6'-bromo-2,2-dimethyl-2'-oxospiro[[1,3]dioxane-5,3'-indoline]-1'-carboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution or tert-butyl 6-bromo-3,3-bis(hydroxymethyl)-2-oxoindoline-1-carboxylate (1.00 g, 2.69 mmol) and 4-methylbenzenesulfonic acid hydrate (0.026 g, 0.134 mmol) in DMF (27 mL) was added 2,2-dimethoxypropane (0.49 mL, 4.03 mmol). The solution was stirred at rt overnight followed by the addition of additional 2,2-dimethoxypropane (0.49 mL, 4.03 mmol) and 4-methylbenzenesulfonic acid hydrate (0.026 g, 0.134 mmol). After stirring at 60° C. for 5 h, the solution was poured into saturated aqueous NaHCO3 and extracted with DCM. The combined organic extracts were purified by column chromatography (eluting with a gradient of 0-30% EtOAc in hexanes) to give tert-butyl 6′-bromo-2,2-dimethyl-2′-oxospiro[[1,3]dioxane-5,3′-indoline]-1′-carboxylate as a white solid. Mass Spectrum (ESI) m/e=434.0 [(M+Na+) (79Br)] and 436.0 [(M+Na+) (81Br)].

Workup

  1. stirringAfter stirring at 60° C. for 5 h
  2. extractionextracted with DCM
  3. customThe combined organic extracts were purified by column chromatography (
  4. washeluting with a gradient of 0-30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-d369e60fc6fe41f7a0504081b443f1cc
Source dataset
uspto-grants-2014_07
Patent number
US08765940B2

Reaction notes

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