Cesium carbonate → Di-tert-butyl (4S)-N-(tert-butoxycarbonyl)-4-{4-[3-(tosyloxy)propoxy]benzyl}-L-glutamate

HRID 591258Notes

Reaction equation

HRID 591258 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:10][C@H:11]([CH2:19][C:20]1[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][CH:21]=1)[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].[C:40]1([CH3:64])[CH:45]=[CH:44][C:43]([S:46]([O:49][CH2:50][CH2:51][CH2:52]OS(C2C=CC(C)=CC=2)(=O)=O)(=[O:48])=[O:47])=[CH:42][CH:41]=1>CN(C)C=O>[C:1]([O:5][C:6]([NH:8][C@H:9]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:10][C@H:11]([CH2:19][C:20]1[CH:25]=[CH:24][C:23]([O:26][CH2:52][CH2:51][CH2:50][O:49][S:46]([C:43]2[CH:42]=[CH:41][C:40]([CH3:64])=[CH:45][CH:44]=2)(=[O:47])=[O:48])=[CH:22][CH:21]=1)[C:12]([O:14][C:15]([CH3:16])([CH3:18])[CH3:17])=[O:13])=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 2303703-(4-Methylphenyl)sulfonyloxypropyl 4-methylbenzenesulfonateHCID 70957078di-tert-butyl (4S)-N-(tert-butoxycarbonyl)-4-(4-hydroxybenzyl)-L-glutamate

Product 1

HCID 70674889Di-tert-butyl (4S)-N-(tert-butoxycarbonyl)-4-{4-[3-(tosyloxy)propoxy]benzyl}-L-glutamate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To 100 mg (0.22 mmol) of di-tert-butyl (4S)—N-(tert-butoxycarbonyl)-4-(4-hydroxy-benzyl)-L-glutamate (Example 1b) in 10 mL N,N-dimethylformamide were added 210 mg (0.64 mmol) of cesium carbonate and 413 mg (1.07 mmol) of 1,3-propanediol di-p-toluenesulfonate (Aldrich) and the resulting suspension was stirred overnight at room temperature. The reaction mixture was then filtered, the solvent evaporated and the residue was taken up in dichloromethane and 1 M hydrochloric acid. The organic phase was separated off, washed with water until neutral, dried over sodium sulfate and filtered, and the filtrate was concentrated in vacuo. The crude product obtained in this manner was chromatographed on silica gel using a hexane/ethyl acetate gradient, and the appropriate fractions were combined and concentrated.

Workup

  1. filtrationThe reaction mixture was then filtered
  2. customthe solvent evaporated
  3. customThe organic phase was separated off
  4. washwashed with water until neutral,
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-bd60d660f8cb4eb9b2f431b4a464a96c
Source dataset
uspto-grants-2016_01
Patent number
US09238631B2

Reaction notes

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