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

HRID 254458Notes

Reaction equation

HRID 254458 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-8cb446b9507a470e83573b8d5b1f93d2
Source dataset
uspto-grants-2011_01
Patent number
US07875638B2

Reaction notes

Loading…