Cornforth reagent → Methyl 4-[bis(tert-butoxy)phosphorylcarbonyl]-N-(benzyloxycarbonyl)-D,L-phenylalaninate

HRID 258169Notes

Reaction equation

HRID 258169 reaction equation
[C:1]([O:5][P:6]([CH:13]([OH:37])[C:14]1[CH:36]=[CH:35][C:17]([CH2:18][CH:19]([C:31]([O:33][CH3:34])=[O:32])[NH:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])=[CH:16][CH:15]=1)([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=O.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>C(Cl)(Cl)Cl.CCOC(C)=O>[C:9]([O:8][P:6]([C:13]([C:14]1[CH:36]=[CH:35][C:17]([CH2:18][CH:19]([C:31]([O:33][CH3:34])=[O:32])[NH:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])=[CH:16][CH:15]=1)=[O:37])([O:5][C:1]([CH3:3])([CH3:2])[CH3:4])=[O:7])([CH3:10])([CH3:11])[CH3:12]

Participants

5

Reactant 2

HCID 2724130Cornforth reagentHCID 10392366Methyl 4-[bis(tert-butoxy)phosphorylhydroxymethyl]-N-(benzyloxycarbonyl)-D,L-phenylalaninate

Product 1

HCID 11756879Methyl 4-[bis(tert-butoxy)phosphorylcarbonyl]-N-(benzyloxycarbonyl)-D,L-phenylalaninateYield 70%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 9 (125 mg, 0.23 mmol) in CHCl3 (1 mL) was added celite (200 mg) and freshly activated 4A molecular sieves (230 mg). Pyridinium dichromate (219 mg, 0.58 mmol) was added and the mixture stirred at ambient temperature (4 hours). The reaction was diluted with EtOAc (5 mL) and filtered through a pad of Florisil (TLC grade). The Florisil was rinsed with EtOAc (30 mL) and combined filtrates taken to dryness by rotary evaporation under reduced pressure to afford crude 10 (85 mg, 70%). Silica gel chromatography [EtOAc/hexanes (1:1)]provided pure 10 (77 mg, 62%).

Workup

  1. filtrationfiltered through a pad of Florisil (TLC grade)
  2. washThe Florisil was rinsed with EtOAc (30 mL)
  3. customtaken to dryness by rotary evaporation under reduced pressure

Sources & evidence

ORD record
ord-87e1d5322a49400ebf043d4eb1d7d592
Source dataset
uspto-grants-1993_11
Patent number
US05264607

Reaction notes

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