2-Methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)-1lambda6-thiane-1,1-dione

HRID 1485767Notes

Reaction equation

HRID 1485767 reaction equation
C([Mg]Cl)(C)C.I[C:7]1[CH:8]=[N:9][N:10]([CH:12]2[CH2:17][CH2:16][S:15](=[O:19])(=[O:18])[CH2:14][CH2:13]2)[CH:11]=1.CO[B:22]1[O:26][C:25]([CH3:28])([CH3:27])[C:24]([CH3:30])([CH3:29])[O:23]1>C1COCC1>[CH3:29][C:24]1([CH3:30])[C:25]([CH3:28])([CH3:27])[O:26][B:22]([C:7]2[CH:8]=[N:9][N:10]([CH:12]3[CH2:17][CH2:16][S:15](=[O:19])(=[O:18])[CH2:14][CH2:13]3)[CH:11]=2)[O:23]1

Participants

5

Reactant 3

HCID 109757592-Methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 1180801974-(4-iodo-1H-pyrazol-1-yl)tetrahydro-2H-thiopyran 1,1-dioxideHCID 178418918HCID 178418918, compound

Product 1

HCID 1239933294-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)-1lambda6-thiane-1,1-dioneYield 68%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Isopropylmagnesium chloride (2.0 M in THF, 1.23 mL, 2.45 mmol) was slowly added to a solution of 4-(4-iodo-1H-pyrazol-1-yl)tetrahydro-2H-thiopyran 1,1-dioxide (0.50 g, 1.533 mmol) in THF (6.0 mL) at −10° C. The reaction mixture was warmed to room temperature and stirred for 1 h. The reaction was then cooled to 0° C., 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.402 mL, 2.45 mmol) was added, and the reaction stirred at room temperature for an additional 1.5 h. The reaction solution was then concentrated in vacuo to remove the THF. The crude solid was dissolved in ether (200 mL) and filtered. The filtrate was slowly concentrated until a white precipitate formed. The solution was allowed to stand for 2 h, and the precipitate was filtered and dried in vacuo to afford 4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)tetrahydro-2H-thiopyran 1,1-dioxide (0.34 g, 68%) as a white powder. MS (ESI, pos. ion) m/z 327 [M+H]+.

Workup

  1. temperatureThe reaction was then cooled to 0° C.
  2. stirringthe reaction stirred at room temperature for an additional 1.5 h
  3. concentrationThe reaction solution was then concentrated in vacuo
  4. customto remove the THF
  5. dissolutionThe crude solid was dissolved in ether (200 mL)
  6. filtrationfiltered
  7. concentrationThe filtrate was slowly concentrated until a white precipitate
  8. customformed
  9. waitto stand for 2 h
  10. filtrationthe precipitate was filtered
  11. customdried in vacuo

Sources & evidence

ORD record
ord-a26b9af0387d4c808aaafe181092af48
Source dataset
uspto-grants-2016_08
Patent number
US09422281B2

Reaction notes

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