HCID 58252548, compound → HCID 58252469, compound

HRID 2403657Notes

Reaction equation

HRID 2403657 reaction equation
[Br:1][CH:2]1[C:10]2([CH2:15][CH2:14][N:13]([C:16]([O:18][CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)=[O:17])[CH2:12][CH2:11]2)[CH2:9][C:8]2[CH:7]=[N:6][N:5]([C:26]([CH3:29])([CH3:28])[CH3:27])[C:4]=2[CH:3]1[OH:30].CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O>CC(C)=O>[Br:1][CH:2]1[C:10]2([CH2:15][CH2:14][N:13]([C:16]([O:18][CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)=[O:17])[CH2:12][CH2:11]2)[CH2:9][C:8]2[CH:7]=[N:6][N:5]([C:26]([CH3:28])([CH3:27])[CH3:29])[C:4]=2[C:3]1=[O:30]

Participants

4

Reactant 2

HCID 58252548HCID 58252548, compoundHCID 131709961Jones' reagent

Product 1

HCID 58252469HCID 58252469, compoundYield 87.1%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Conditions

Temperature
0 °C

Procedure

Benzyl 6-bromo-1-tert-butyl-7-hydroxy-1,4,6,7-tetrahydrospiro[indazole-5,4′-piperidine]-1′-carboxylate (57.9 g, 122 mmol) was dissolved in acetone (1 L) and cooled to 0° C. in an ice bath. To the solution was added Jones Reagent (122 mL) (Fillion, E. Tetrahedron Letters 2004, 46, 1091-1094). The ice bath was removed and the reaction was allowed to warm to room temperature and stir for 45 minutes. Saturated aqueous sodium bicarbonate was added until gas evolution ceased and the pH reached 7. The resulting mixture was filtered through a pad of Celite®, rinsing with ethyl acetate. The filtrate layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed twice with water, once with saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and concentrated. The residue was crystallized from ethyl acetate/heptanes to afford the title compound (50.4 g, 87%). +ESI (M+H) 474.5; 1H NMR (400 MHz, CDCl3, δ): 7.32 (d, J=9.38 Hz, 6 H), 5.11 (s, 2 H), 4.24 (s, 1 H), 3.58-3.84 (m, 2 H), 3.16-3.41 (m, 2 H), 2.67-2.91 (m, 2 H), 1.80 (br. s., 1 H), 1.61-1.76 (m, 11 H), 1.52-1.61 (m, 1 H).

Workup

  1. customThe ice bath was removed
  2. temperatureto warm to room temperature
  3. additionSaturated aqueous sodium bicarbonate was added until gas evolution
  4. filtrationThe resulting mixture was filtered through a pad of Celite®
  5. washrinsing with ethyl acetate
  6. customThe filtrate layers were separated
  7. extractionthe aqueous layer was extracted with ethyl acetate
  8. washThe combined organic extracts were washed twice with water, once with saturated aqueous sodium chloride
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe residue was crystallized from ethyl acetate/heptanes

Sources & evidence

ORD record
ord-fd09adc68b154658a7d6aff71f645197
Source dataset
uspto-grants-2014_08
Patent number
US08802688B2

Reaction notes

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