Acetate → HCID 50942718, compound

HRID 571138Notes

Reaction equation

HRID 571138 reaction equation
[C:1]([O-:4])(=[O:3])[CH3:2].N1[C:10]([CH3:11])=[CH:9][CH:8]=[CH:7][C:6]=1[CH3:12].[Si:13]([O:20]S(C(F)(F)F)(=O)=O)([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14].C([O-])(O)=O.[Na+]>C(Cl)Cl>[C:1]([O:4][CH2:12][CH2:6][C@@H:7]1[CH:8]=[CH:9][CH2:10][C@@H:11]1[O:20][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 175AcetateHCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 516892Sodium Bicarbonate

Product 1

HCID 50942718HCID 50942718, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of the above acetate (54 mg, 0.32 mmol) and 2,6-lutidine (74 μL, 0.63 mmol) in CH2Cl2 (1 mL) was added tert-butyldimethylsilyltrifluoromethanesulfonate (125 mg, 108 μL) at −78° C. under argon. The mixture was stirred for 10 min at which point reaction completion was observed. Sat. aq. NaHCO3 solution (1 mL) and additional CH2Cl2 (2 mL) were added. The two layers were separated and the aqueous layer was further extracted with CH2Cl2 (2×2 mL). The combined organic layer was washed with brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The crude oil was purified by column chromatography on silica gel using hexanes/EtOAc (20:1) as the eluent to afford silylated product 5 (90 mg, >99%) as a colorless oil. TLC: Rf=0.68 (hexanes/EtOAc=3:1); 1H NMR (CDCl3, 300 MHz) δ 5.68 (s, 2H), 4.45 (dt, J=5.1, 6.3 Hz, 1H), 4.14 (t, J=6.9 Hz, 2H), 2.67-2.55 (m, 1H), 2.47 (dd, J=6.9, 15.4 Hz, 1H), 2.23 (dd, J=4.8, 15.4 Hz, 1H), 2.04 (s, 3H), 2.01-1.85 (m, 1H), 1.72-1.56 (m, 1H), 0.88 (s, 9H), 0.06 (s, 6H); 13C NMR (CDCl3, 75 MHz) δ 171.2, 132.7, 128.4, 73.6, 63.8, 45.9, 41.0, 27.4, 25.8, 21.0, 18.1, −4.6, −5.0.

Workup

  1. customThe two layers were separated
  2. extractionthe aqueous layer was further extracted with CH2Cl2 (2×2 mL)
  3. washThe combined organic layer was washed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude oil was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-e79e38e900ee46cc9e2c1dd3c1281b0b
Source dataset
uspto-grants-2015_05
Patent number
US09024038B2

Reaction notes

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