Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → HCID 86667443, compound

HRID 75009Notes

Reaction equation

HRID 75009 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([NH:8][C@H:9]2[CH2:14][CH2:13][CH2:12][C:11](=O)[CH2:10]2)[C:5]([F:16])=[CH:4][N:3]=1.C1(P(C2C=CC=CC=2)(C2C=CC=CC=2)=[CH:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])C=CC=CC=1>C1(C)C=CC=CC=1>[Cl:1][C:2]1[N:7]=[C:6]([NH:8][C@H:9]2[CH2:14][CH2:13][CH2:12][C:11](=[CH:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:10]2)[C:5]([F:16])=[CH:4][N:3]=1

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 86667417(S)-3-(2-chloro-5-fluoropyrimidin-4-ylamino)cyclohexanone

Product 1

HCID 86667443HCID 86667443, compoundYield 99.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of (3S)-3-[(2-chloro-5-fluoro-pyrimidin-4-yl)amino]cyclohexanone (29b) (2.00 g, 8.21 mmol) in toluene (40 mL) was added ethyl 2-triphenylphosphoranylideneacetate (4.29 g, 12.31 mmol). The reaction was refluxed overnight then concentrated in vacuo and purified by silica gel chromatography (Hexanes:EtOAc). The desired product eluted at 15% ethyl acetate. Clean fractions were combined and concentrated to give 2.57 g of 62a. LCMS+: 314.18 at 3.75 min (10-90% MeOH, 3/5 grad/run, Formic Acid).

Workup

  1. temperatureThe reaction was refluxed overnight
  2. concentrationthen concentrated in vacuo
  3. custompurified by silica gel chromatography (Hexanes:EtOAc)
  4. washThe desired product eluted at 15% ethyl acetate
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-606491bcd3d044b0bb35d5a24fed6259
Source dataset
uspto-grants-2014_09
Patent number
US08829007B2

Reaction notes

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