Triphenylphosphine → HCID 118093072, compound

HRID 708918Notes

Reaction equation

HRID 708918 reaction equation
[F:1][C:2]1[C:3]([OH:21])=[C:4]([CH:15]=[C:16]([N+:18]([O-])=O)[CH:17]=1)[CH2:5][N:6]([CH3:14])C(=O)OC(C)(C)C.[CH3:22][O:23][CH2:24][C@H:25](O)[CH3:26].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.[Cl-:61].[NH4+]>C1COCC1.[Zn]>[ClH:61].[ClH:61].[F:1][C:2]1[CH:17]=[C:16]([CH:15]=[C:4]([CH2:5][NH:6][CH3:14])[C:3]=1[O:21][C@@H:25]([CH3:26])[CH2:24][O:23][CH3:22])[NH2:18]

Participants

8

Reactant 5

HCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 2733589(R)-(-)-1-Methoxy-2-propanolHCID 5363146Diisopropyl azodicarboxylateHCID 70292396HCID 70292396, compound

Product 1

HCID 118093072HCID 118093072, compoundYield 89.1%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 17D (556 mg, 1.852 mmol), (R)-1-methoxypropan-2-ol (367 mg, 4.07 mmol), triphenylphosphine (1068 mg, 4.07 mmol) in THF (5 mL) was added DIAD (0.81 mL, 4.07 mmol). The reaction mixture was stirred at 0° C. for 30 min, and at rt for 16 h. The mixture was concentrated and purified by flash chromatography. The desired fractions were combined and concentrated. The residue was dissolved in MeOH (30 mL) and THF (10 mL). Zinc (dust) (3.47 g, 53.1 mmol) and ammonium chloride (5.68 g, 106 mmol) were added. The resulting solution was stirred at rt for 2 h. MeOH was removed under reduced pressure. Na2CO3 (aq, 100 mL) and EtOAc (150 mL) was added, and the suspension was stirred vigorously for 10 min. The mixture was filtered through a glass frit, solid residue was washed with EtOAc (3×150 mL). Combined EtOAc fractions were washed with std. Na2CO3 (aq, 2×50 mL), water (2×50 mL), brine (1×50 mL) and dried (Na2SO4). EtOAc was removed under reduced pressure and the residue was dissolved in EtOAc (10 mL), treated with HCl (4M, 8 mL) for 2 h at rt. The solvent was removed under reduced pressure to yield 37A (520 mg, 1.650 mmol, 89% yield) as a yellow solid. MS (ESI) m/z: 244.3 (M+H)+.

Workup

  1. waitat rt for 16 h
  2. concentrationThe mixture was concentrated
  3. custompurified by flash chromatography
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in MeOH (30 mL)
  6. stirringThe resulting solution was stirred at rt for 2 h
  7. customMeOH was removed under reduced pressure
  8. additionNa2CO3 (aq, 100 mL) and EtOAc (150 mL) was added
  9. stirringthe suspension was stirred vigorously for 10 min
  10. filtrationThe mixture was filtered through a glass frit, solid residue
  11. washwas washed with EtOAc (3×150 mL)
  12. washCombined EtOAc fractions were washed with std
  13. dry with materialNa2CO3 (aq, 2×50 mL), water (2×50 mL), brine (1×50 mL) and dried (Na2SO4)
  14. customEtOAc was removed under reduced pressure
  15. dissolutionthe residue was dissolved in EtOAc (10 mL)
  16. additiontreated with HCl (4M, 8 mL) for 2 h at rt
  17. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-018cae9d99ee4c8abf90e085ba6cb144
Source dataset
uspto-grants-2015_11
Patent number
US09174974B2

Reaction notes

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