4-Nitrobenzoic Acid → (6S,7R)-2,2,3,3,11,11-hexamethyl-9-oxo-7-phenyl-4,10-dioxa-8-aza-3-siladodecan-6-yl 4-nitrobenzoate

HRID 64435Notes

Reaction equation

HRID 64435 reaction equation
[C:1]([O:5][C:6](=[O:26])[NH:7][C@H:8]([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C@@H:9]([OH:19])[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:46]([C:49]1[CH:57]=[CH:56][C:52]([C:53](O)=[O:54])=[CH:51][CH:50]=1)([O-:48])=[O:47].N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1(C)C=CC=CC=1>C1COCC1.C(OCC)(=O)C.O>[N+:46]([C:49]1[CH:50]=[CH:51][C:52]([C:53]([O:19][C@@H:9]([C@@H:8]([C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[NH:7][C:6](=[O:26])[O:5][C:1]([CH3:2])([CH3:3])[CH3:4])[CH2:10][O:11][Si:12]([CH3:13])([CH3:14])[C:15]([CH3:16])([CH3:17])[CH3:18])=[O:54])=[CH:56][CH:57]=1)([O-:48])=[O:47]

Participants

8

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 10738641tert-butyl[(1R,2R)-3-{[tert-butyl(dimethyl)silyl]oxy}-2-hydroxy-1-phenylpropyl]carbamateHCID 66880968DIAD toluene

Product 1

HCID 86713450(6S,7R)-2,2,3,3,11,11-hexamethyl-9-oxo-7-phenyl-4,10-dioxa-8-aza-3-siladodecan-6-yl 4-nitrobenzoateYield 65.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 700 mg of tert-butyl[(1R,2R)-3-{[tert-butyl(dimethyl)silyl]oxy}-2-hydroxy-1-phenylpropyl]carbamate in 35 ml of THF was added 1.2 g of triphenylphosphine, 766 mg of 4-nitrobenzoic acid, and 2.4 ml of a 1.9 M diisopropyl azodicarboxylate/toluene solution under ice-cooling, followed by stirring at room temperature for 5 hours. To the reaction mixture were added water and ethyl acetate to carry out a layer separation operation. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 638 mg of (6S,7R)-2,2,3,3,11,11-hexamethyl-9-oxo-7-phenyl-4,10-dioxa-8-aza-3-siladodecan-6-yl 4-nitrobenzoate.

Workup

  1. temperaturecooling
  2. customa layer separation operation
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customthe solvent was evaporated under reduced pressure
  6. customThe obtained residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-3400f52d25304f91b1f8c251a22a3f58
Source dataset
uspto-grants-2016_09
Patent number
US09447090B2

Reaction notes

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