2,6-Lutidine → 9-Benzyloxy-7-(tert-butyldimethylsilanyloxy)-3-(diethylmethylsilanyloxy)-4,4,6,8-tetramethyl-5-oxo-nonanoic acid tert-butyl ester

HRID 131619Notes

Reaction equation

HRID 131619 reaction equation
[C:1]([O:5][C:6](=[O:36])[CH2:7][CH:8]([O:29][Si:30]([CH2:34][CH3:35])([CH2:32][CH3:33])[CH3:31])[C:9]([CH3:28])([CH3:27])[C:10](=[O:26])[CH:11]([CH3:25])[CH:12]([OH:24])[CH:13]([CH3:23])[CH2:14][O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)([CH3:4])([CH3:3])[CH3:2].N1C(C)=CC=CC=1C.[Si:45](OS(C(F)(F)F)(=O)=O)([C:48]([CH3:51])([CH3:50])[CH3:49])([CH3:47])[CH3:46]>C(Cl)Cl.C([O-])(O)=O.[Na+]>[C:1]([O:5][C:6](=[O:36])[CH2:7][CH:8]([O:29][Si:30]([CH2:34][CH3:35])([CH2:32][CH3:33])[CH3:31])[C:9]([CH3:27])([CH3:28])[C:10](=[O:26])[CH:11]([CH3:25])[CH:12]([O:24][Si:45]([C:48]([CH3:51])([CH3:50])[CH3:49])([CH3:47])[CH3:46])[CH:13]([CH3:23])[CH2:14][O:15][CH2:16][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonate2×HCID 668507919-Benzyloxy-3-(diethylmethylsilanyloxy)-7-hydroxy-4,4,6,8-tetramethyl-5-oxo-nonanoic Acid Tert-Butyl Ester

Product 1

HCID 668507769-Benzyloxy-7-(tert-butyldimethylsilanyloxy)-3-(diethylmethylsilanyloxy)-4,4,6,8-tetramethyl-5-oxo-nonanoic acid tert-butyl esterYield 111.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of 71a (4.1 mg, 7.6 μmol) and 2,6-lutidine (10.0 μL, 43.5 mmol) in CH2Cl2 (0.2 mL) at −78° C. was added TBSOTf (10.0 μL, 85.8 mmol). After 2 h, more, 6-lutidine (10.0 μL, 43.5 mmol) and TBSOTf (10.0 μL, 85.8 mmol) were added. After 6 h, the mixture was diluted with sat aq NaHCO3. The aqueous layer was extracted three times with EtOAc. The combined organic extracts were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The crude product was purified by flash chromatography (gradient hexane to hexane/EtOAc 91:9) to give 36 (5.4 mg, 82%) as a clear oil. Spectroscopic data agreed well with the reported values.

Workup

  1. waitAfter 6 h
  2. extractionThe aqueous layer was extracted three times with EtOAc
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product was purified by flash chromatography (gradient hexane to hexane/EtOAc 91:9)

Sources & evidence

ORD record
ord-666a441ebc8245a495b7cb36a46cf723
Source dataset
uspto-grants-2008_06
Patent number
US07384964B2

Reaction notes

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