Triphenylphosphine → Methyl 3-{[(1S)-1-methylpropyl]oxy}-5-[(phenylmethyl)oxy]benzoate

HRID 1990161Notes

Reaction equation

HRID 1990161 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.[OH:15][C:16]1[CH:17]=[C:18]([CH:23]=[C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:25]=1)[C:19]([O:21][CH3:22])=[O:20].[CH3:34][CH2:35][C@H:36](O)[CH3:37].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1.C(OCC)C>[CH3:34][C@H:35]([O:15][C:16]1[CH:17]=[C:18]([CH:23]=[C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:25]=1)[C:19]([O:21][CH3:22])=[O:20])[CH2:36][CH3:37]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 84682(-)-2-ButanolHCID 5363146Diisopropyl azodicarboxylateHCID 7472028Methyl 3-(benzyloxy)-5-hydroxybenzoate

Product 1

HCID 59127096Methyl 3-{[(1S)-1-methylpropyl]oxy}-5-[(phenylmethyl)oxy]benzoateYield 84.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of DIAD (16.6 mL, 84.0 mmol) in dry THF (100 mL) was added dropwise to a cooled (ice bath) stirred mixture of methyl 3-hydroxy-5-{[phenylmethyl]oxy}benzoate (14.5 g, 56.2 mmol); R-(−)-sec-butanol (5 g, 67.0 mmol) and solid-supported triphenylphosphine (28 g, of 3 mmol per g loading, 84.0 mmol) in dry THF (400 mL) whilst maintaining the temperature below 10° C. The mixture was allowed to stir for 3 hours, then diluted with diethyl ether (800 mL) and filtered. Removal of the solvent gave a pale coloured oil, which was purified by column chromatography on silica, eluting with 25% ethyl acetate in hexane; to give the desired product (14.87 g).

Workup

  1. temperaturea cooled (ice bath)
  2. stirringto stir for 3 hours
  3. filtrationfiltered
  4. customRemoval of the solvent
  5. customgave a pale coloured oil, which
  6. customwas purified by column chromatography on silica
  7. washeluting with 25% ethyl acetate in hexane

Sources & evidence

ORD record
ord-72942992e87d443b9a6fe3a84c8a7ac4
Source dataset
uspto-grants-2010_01
Patent number
US07642259B2

Reaction notes

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