Cerous carbonate → (S)-tert-butyl 2-((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)methyl)morpholine-4-carboxylate

HRID 1498838Notes

Reaction equation

HRID 1498838 reaction equation
CS(O[CH2:6][C@H:7]1[O:12][CH2:11][CH2:10][N:9]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:8]1)(=O)=O.[CH3:20][C:21]1([CH3:33])[C:25]([CH3:27])([CH3:26])[O:24][B:23]([C:28]2[CH:29]=[N:30][NH:31][CH:32]=2)[O:22]1.C(=O)([O-])[O-].[Ce+3].C(=O)([O-])[O-].C(=O)([O-])[O-].[Ce+3]>C(#N)C>[CH3:20][C:21]1([CH3:33])[C:25]([CH3:26])([CH3:27])[O:24][B:23]([C:28]2[CH:32]=[N:31][N:30]([CH2:6][C@H:7]3[O:12][CH2:11][CH2:10][N:9]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH2:8]3)[CH:29]=2)[O:22]1

Participants

5

Reactant 3

HCID 160516Cerous carbonateHCID 27740104-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 86673567(S)-tert-butyl 2-((methylsulfonyloxy)methyl)morpholine-4-carboxylate

Product 1

HCID 123262148(S)-tert-butyl 2-((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)methyl)morpholine-4-carboxylateYield 52.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

To a mixture of (S)-tert-butyl 2-((methylsulfonyloxy)methyl)morpholine-4-carboxylate (430 mg, 1.46 mmol) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (283 mg, 1.46 mmol) in 50 mL of acetonitrile was added cerium carbonate (1.43 g, 4.37 mmol), and the mixture was stirred at 60° C. for 3 h. TLC and LCMS showed the reaction was completed. After the solvents were removed under reduced pressure, the residue was diluted with 50 mL of ethyl acetate, and washed with water (50 mL×3) and brine. The organic layer was separated, dried over sodium sulfate, filtered and concentrated. The crude product was purified by silica gel chromatography (petroleum ether:ethyl acetate=5:1) to get the title product (300 mg, 52%) as colorless oil. MS (ES+) C19H32BN3O5 requires: 393. found: 394 [M+H]+.

Workup

  1. customAfter the solvents were removed under reduced pressure
  2. additionthe residue was diluted with 50 mL of ethyl acetate
  3. washwashed with water (50 mL×3) and brine
  4. customThe organic layer was separated
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified by silica gel chromatography (petroleum ether:ethyl acetate=5:1)

Sources & evidence

ORD record
ord-e943a5067c014b4ba4e657bbf87c2da6
Source dataset
uspto-grants-2015_12
Patent number
US09200002B2

Reaction notes

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