Phosphate → HCID 69904252, compound

HRID 2287525Notes

Reaction equation

HRID 2287525 reaction equation
[Si:1]([N:8]1[C@@H:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C@H:10]([CH2:18][C:19]([CH2:21][O:22]C(=O)C2C=CC(OC)=CC=2)=[CH2:20])[C:9]1=[O:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].P([O-])([O-])([O-])=O.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C(Cl)Cl>[Si:1]([N:8]1[C@@H:11]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[C@H:10]([CH2:18][C:19]([CH2:21][OH:22])=[CH2:20])[C:9]1=[O:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 1061PhosphateHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 70300000HCID 70300000, compound

Product 1

HCID 69904252HCID 69904252, compoundYield 160.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred mixture of (3S*,4R*)-1-tert-Butyldimethylsilyl-3-[2-(4-methoxybenzoyloxy)methyl-2-propenyl]-4-phenyl-2-azetidinone (18.74 g, 41.5 mmol), pH7 phosphate buffer (15.0 ml), and CH2Cl2 (250 ml) was added 2,3-dichloro-5.6-dicyano-1,4-benzoquinone (DDQ, 15.1 g, 66.4 mmol) portionwise at room temperature; on the addition, the reaction mixture became dark green, and then red solids precipitated with stirring. (In the course of addition, a slight heat evolution was observed.) The stirring was continued at room temperature for two hours, the reaction being monitored by TLC[Merck Kieselgel 60, n-hexane-AcOEt (3:1)]. sat. NaHCO3 aq. solution (80.0 ml) was added to quench the reaction, wherein gas evolution was observed. After Celite was added, the mixture was filtered through a pad of Celite, and the filter cake was washed with CH2Cl2. The combined filtrate and CH2Cl2 washings were washed with sat. NaHCO3 aq. solution (×2), and dried (MgSO4). The combined aqueous washings were filtered through a pad of Celite, and the filter cake was washed with CH2Cl2. From the combined filtrate and washings, the CH2Cl2 layer was separated, and the aqueous layer was extracted with CH2Cl2 (100 ml×3). The combined CH2Cl2 layer and washings were dried (MgSO4). The CH2Cl2 solution dried were combined, treated with activated charcoal, and concentrated in vacuo to give an orange oil (22.1 g). This was flash chromatographed over SiO2 (Merck Kieselgel 60, 200 g). Elution with n-hexane-AcOEt (15:1/5:1/3:1) gave title compound (11.18 g, 81.2%) as a viscous pale yellow oil. IRmax (film): 3420(s), 1750(s), 1733(s), 1718(s), 1705(s), 1650(m), 1040(s), 900(s), 775(s) 700(s) cm-1 ; 1H-NMR δ: 7.43-7.25(m, 5H), 5.04(br.s, 1H), 4.82(br.s, 1H), 4.20(d, J=2.2 Hz, 1H), 4.06(br.s, 2H), 3.26(ddd, J=8.2, 7.0, 2.2 Hz, 1H), 2.67(dd, J=15.2, 7.0 Hz, 1H), 2.54(dd, J=15.2, 8.2 Hz, 1H), 2.42(br.s, 1H, OH), 0.92(s, 9H), 0.21(s, 3H), -0.19(s, 3H) ppm.

Workup

  1. additionon the addition
  2. customred solids precipitated
  3. addition(In the course of addition
  4. additionsat. NaHCO3 aq. solution (80.0 ml) was added
  5. customto quench
  6. customthe reaction, wherein gas evolution
  7. additionAfter Celite was added
  8. filtrationthe mixture was filtered through a pad of Celite
  9. washthe filter cake was washed with CH2Cl2
  10. washThe combined filtrate and CH2Cl2 washings were washed with sat. NaHCO3 aq. solution (×2)
  11. dry with materialdried (MgSO4)
  12. filtrationThe combined aqueous washings were filtered through a pad of Celite
  13. washthe filter cake was washed with CH2Cl2
  14. customFrom the combined filtrate and washings, the CH2Cl2 layer was separated
  15. extractionthe aqueous layer was extracted with CH2Cl2 (100 ml×3)
  16. dry with materialThe combined CH2Cl2 layer and washings were dried (MgSO4)
  17. dry with materialThe CH2Cl2 solution dried
  18. additiontreated with activated charcoal
  19. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1906ada2153f4382872ceaa353f3a926
Source dataset
uspto-grants-2000_07
Patent number
US06083943

Reaction notes

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