Water → HCID 59271809, compound

HRID 1893193Notes

Reaction equation

HRID 1893193 reaction equation
[C:1]([Si:5]([O:8][CH2:9][C:10]([O:15][CH3:16])([CH3:14])[CH2:11][CH:12]=[CH2:13])([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].O.B1([O-])O[O:19]1.O.O.O.O.[Na+]>C1COCC1>[Si:5]([O:8][CH2:9][C:10]([O:15][CH3:16])([CH3:14])[CH2:11][CH2:12][CH2:13][OH:19])([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:6])[CH3:7]

Participants

5

Reactant 3

HCID 962WaterHCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrateHCID 59271891HCID 59271891, compound

Product 1

HCID 59271809HCID 59271809, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of tert-butyl [(2-methoxy-2-methylpent-4-en-1-yl)oxy]dimethylsilane (2.45 kg, 10.04 mol) in THF (3.5 L) at <5° C. was added BH3 in THF (1M solution, 11.05 L, 11.05 mol) via a funnel while maintaining the reaction temperature at <15° C. The reaction mixture was stirred for 30 minutes and quenched with water (11.75 L, 652 mol). To the stirred mixture was added sodium perborate tetrahydrate (4.64 kg, 30.2 mol) and the mixture was stirred overnight at ambient temperature. The reaction mixture was then filtered, and the filter cake washed with 14 L MTBE. The combined organic layers were washed with brine/water (7 L/3 L). The aqueous layer was extracted with MTBE (14 L). The combined organic layers were sequentially washed with 18.75 L of 5% aqueous sodium thiosulfate/brine/water (10 L/5 L/3.75 L) and then concentrated in vacuo to provide crude material. Flash column chromatography (multiple runs) eluted with 0% to 100% DCM in heptane, then 1% to 50% EtOAc in DCM provided the desired alcohol. 1H NMR (300 MHz, CDCl3): δ 3.65-3.59 (m, 2 H); 3.47 (dd, J=23.9, 10.1 Hz, 2 H); 3.24 (s, 3 H); 2.21-2.07 (m, 1 H); 1.63-1.54 (m, 4 H); 1.05-0.70 (m, 9 H); 0.04 (s, 6H).

Workup

  1. temperaturewhile maintaining the reaction temperature at <15° C
  2. stirringthe mixture was stirred overnight at ambient temperature
  3. filtrationThe reaction mixture was then filtered
  4. washthe filter cake washed with 14 L MTBE
  5. washThe combined organic layers were washed with brine/water (7 L/3 L)
  6. extractionThe aqueous layer was extracted with MTBE (14 L)
  7. washThe combined organic layers were sequentially washed with 18.75 L of 5% aqueous sodium thiosulfate/brine/water (10 L/5 L/3.75 L)
  8. concentrationconcentrated in vacuo
  9. customto provide crude material
  10. washFlash column chromatography (multiple runs) eluted with 0% to 100% DCM in heptane

Sources & evidence

ORD record
ord-4cfb1743909a444596cd7dd493818c9a
Source dataset
uspto-grants-2013_08
Patent number
US08513234B2

Reaction notes

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