Trimethylphosphine → HCID 58460211, compound

HRID 1946492Notes

Reaction equation

HRID 1946492 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][N:10]2[C:14]3[CH:15](O)[CH2:16][CH2:17][C:13]=3[N:12]=[C:11]2[CH:19]([CH3:21])[CH3:20])[CH:5]=[CH:6][C:7]=1[Cl:8].[CH2:22]([O:24][C:25]([CH:27]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[O:26])[CH3:23].CP(C)C.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1(C)C=CC=CC=1.O1CCCC1>[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][N:10]2[C:14]3[CH:15]([C:27]([C:33]([O:35][CH2:36][CH3:37])=[O:34])([C:25]([O:24][CH2:22][CH3:23])=[O:26])[C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH2:16][CH2:17][C:13]=3[N:12]=[C:11]2[CH:19]([CH3:21])[CH3:20])[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

7

Reactant 4

HCID 68983TrimethylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 80471Triethyl methanetricarboxylateHCID 58460192HCID 58460192, compound

Product 1

HCID 58460211HCID 58460211, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of Intermediate 22 (660 mg) and triethylmethanetricarboxylate (0.86 ml) in toluene (1.5 ml) and tetrahydrofuran (1.5 ml), stirred at RT under an inert atmosphere of nitrogen, was added dropwise trimethylphosphine, 1M in toluene (4.06 ml). The resulting solution was cooled to −78° C. and diisopropyl azodicarboxylate (0.799 ml) was added dropwise via syringe and the reaction was stirred at −78° C. for 2 hours. The reaction mixture was removed from the cold bath and allowed to warm to RT and stirred under N2 atmosphere for 30 mins. Reaction mixture concentrated in vacuo. The residue was taken up in DCM (40 ml) and washed with water (40 mL). The 2 phases were separated; the organic extract was dried (hydrophobic frit) and concentrated under vacuum. The residue was purified on silica using a cyclohexane:ethyl acetate 0-100% gradient. The desired fractions were combined and concentrated under vacuum to give the title compound (750 mg). LC/MS MH+ 539, 541, Rt 2.19 min (5 minute run).

Workup

  1. customThe reaction mixture was removed from the cold bath
  2. temperatureto warm to RT
  3. stirringstirred under N2 atmosphere for 30 mins
  4. customReaction mixture
  5. concentrationconcentrated in vacuo
  6. washwashed with water (40 mL)
  7. customThe 2 phases were separated
  8. extractionthe organic extract
  9. customwas dried (hydrophobic frit)
  10. concentrationconcentrated under vacuum
  11. customThe residue was purified on silica using a cyclohexane
  12. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-032bfd621a5f4f64aae4bfced6faebb2
Source dataset
uspto-grants-2013_03
Patent number
US08399444B2

Reaction notes

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