tert-Butyl methyl ether → HCID 90413083, compound

HRID 1746640Notes

Reaction equation

HRID 1746640 reaction equation
C([Si]([O:18][C@@H:19]1[C@H:26]2[C@H:22]([O:23][C:24]([CH3:28])([CH3:27])[O:25]2)[C:21]([CH2:29][O:30][C:31]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)=[C:20]1[F:50])(C1C=CC=CC=1)C1C=CC=CC=1)(C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(OC)(C)C.[O-][Mn](=O)(=O)=O.[K+]>C1COCC1>[F:50][C:20]1[C@H:19]([OH:18])[C@@H:26]2[O:25][C:24]([CH3:28])([CH3:27])[O:23][C@@H:22]2[C:21]=1[CH2:29][O:30][C:31]([C:38]1[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=1)([C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1

Participants

6

Reactant 4

HCID 15413tert-Butyl methyl etherHCID 516875Potassium PermanganateHCID 2724141Tetrabutylammonium FluorideHCID 86268842HCID 86268842, compound

Product 1

HCID 90413083HCID 90413083, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
22.5 °C

Procedure

Compound 9 (1370 g, 1 wt, 1 eq) was dissolved in THF (5.5 L, 4 vol). TBAF (tetra-n-butylammonium fluoride) 1.0 M in THF (2.20 L, 1.61 vol) was added in one portion (not exothermic) and the resulting solution stirred at 20 to 25° C. After 2 h, TLC analysis (70:30 heptanes:TBME (methyl tert-butyl ether) 7:3, KMnO4 visualisation) indicated the reaction was complete by absence of starting material. The reaction mixture was concentrated to an oil under reduced pressure at 40° C. (water bath) on a rotary evaporator until solvent collection ceased. The residue was dissolved in TBME (11.0 L, 8 vol) and subsequently washed with water (2×4.1 L, 2×3 vol) and saturated sodium hydrogen carbonate (4.1 L, 3 vol). The organic phase was dried over Na2SO4 (1.37 kg, 1 wt), filtered and the cake washed with TBME (1.37 L×2,2×1 vol). The combined filtrates were concentrated under reduced pressure at up to 40° C. (water bath) on a rotary evaporator until the TBME content was <5% w/w by 1H NMR to give 10 as a thick pale yellow/orange oil. 1H-NMR (400 MHz, CDCl3) δ 7.7 ppm (d, 4H) TBDPS-F, 7.2-7.5 ppm, (m, 21H) Trityl and TBDPS-F, 5.1 ppm, (t, J=6.3 Hz, 1H) (CH), 4.7 ppm, (m, J=3.5 Hz, 1H) (CH), 4.4 ppm, broad (t, 6.3 Hz, 1H) (CH), 3.9 ppm, (d, J=11.9 Hz) 1H, 3.8 ppm, (d, J=9.9 Hz, 1.7 Hz, 1H) (CH2), δ 2.8 ppm, (d, J=9.4 Hz, 1H) (OH), 81.48 ppm, s, 3H CH3 Acetonide, 51.46 ppm, s, 3H CH3 Acetonide, δ 1.1 pm, s, 9H TBDPS-F (3×CH3), Solvents δ 3.2 ppm, 1.2 ppm TBME, δ 3.7 ppm, 1.7 ppm THF.

Workup

  1. concentrationThe reaction mixture was concentrated to an oil under reduced pressure at 40° C. (water bath)
  2. customon a rotary evaporator
  3. customuntil solvent collection
  4. dissolutionThe residue was dissolved in TBME (11.0 L, 8 vol)
  5. washsubsequently washed with water (2×4.1 L, 2×3 vol) and saturated sodium hydrogen carbonate (4.1 L, 3 vol)
  6. dry with materialThe organic phase was dried over Na2SO4 (1.37 kg, 1 wt)
  7. filtrationfiltered
  8. washthe cake washed with TBME (1.37 L×2,2×1 vol)
  9. concentrationThe combined filtrates were concentrated under reduced pressure at up to 40° C. (water bath)
  10. customon a rotary evaporator until the TBME content

Sources & evidence

ORD record
ord-c4c7a6efb8b241c59a9b66a1cad6fa57
Source dataset
uspto-grants-2015_10
Patent number
US09150520B2

Reaction notes

Loading…