Trichloroacetyl isocyanate → HCID 86760457, compound

HRID 459073Notes

Reaction equation

HRID 459073 reaction equation
[CH:1]1([CH2:6][C:7](=[O:48])/[CH:8]=[CH:9]\[C@H:10]([CH3:47])[C@H:11]([O:39][Si:40]([C:43]([CH3:46])([CH3:45])[CH3:44])([CH3:42])[CH3:41])[C@@H:12]([CH3:38])/[CH:13]=[C:14](/[CH3:37])\[CH2:15][C@H:16]([CH3:36])[C@@H:17]([O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[C@H:18]([CH3:27])[C@@H:19]([OH:26])[C@@H:20]([CH3:25])/[CH:21]=[CH:22]\[CH:23]=[CH2:24])[CH2:5][CH2:4][CH2:3][CH2:2]1.ClC(Cl)(Cl)[C:51]([N:53]=C=O)=[O:52]>C(Cl)Cl>[NH2:53][C:51]([O:26][C@@H:19]([C@@H:20]([CH3:25])/[CH:21]=[CH:22]\[CH:23]=[CH2:24])[C@@H:18]([CH3:27])[C@H:17]([O:28][Si:29]([C:32]([CH3:33])([CH3:34])[CH3:35])([CH3:30])[CH3:31])[C@@H:16]([CH3:36])[CH2:15]/[C:14](/[CH3:37])=[CH:13]\[C@H:12]([CH3:38])[C@@H:11]([O:39][Si:40]([C:43]([CH3:44])([CH3:45])[CH3:46])([CH3:42])[CH3:41])[C@@H:10]([CH3:47])/[CH:9]=[CH:8]\[C:7](=[O:48])[CH2:6][CH:1]1[CH2:5][CH2:4][CH2:3][CH2:2]1)=[O:52]

Participants

4

Reactant 2

HCID 76400Trichloroacetyl isocyanateHCID 86596749HCID 86596749, compound

Product 1

HCID 86760457HCID 86760457, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
23 °C

Procedure

A solution of (3Z,5S,6S,7S,8Z,11S,12R,13R,14S,15S,16Z)-1-cyclopentyl-6,12-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-14-hydroxy-5,7,9,11,13,15-hexamethyl-3,8,16,18-nonadecatetraen-2-one (420 mg, 0.60 mmol, 1 eq) in CH2Cl2 (10 mL) is treated with trichloroacetyl isocyanate (135 mg, 0.72 mmol, 1.2 eq) at 23° C. (20 minutes). The solution is concentrated, and the residue dissolved in CH3OH (10 mL). To this solution is added K2CO3 (0.2 g) and the mixture is stirred at 23° C. (3 hours). The reaction mixture is concentrated and the residue dissolved in Et2O (20 mL). The organic solution is washed with H2O (1×10 mL) and brine (1×20 mL). The aqueous layer is extracted with Et2O (3×10 mL) and the combined extracts are dried (Na2SO4) and concentrated. Chromatography (SiO2, 30–50% EtOAc-hexanes gradient elution) provides (3Z,5S,6S,7S,8Z,11S,12R,13R,14S,15S,16Z)-14-[(aminocarbonyl)oxy]-1-cyclopentyl-6,12-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-5,7,9,11,13,15-hexamethyl-3,8,16,18-nonadecatetraen-2-one (420 mg, 94%).

Workup

  1. concentrationThe solution is concentrated
  2. dissolutionthe residue dissolved in CH3OH (10 mL)
  3. additionTo this solution is added K2CO3 (0.2 g)
  4. concentrationThe reaction mixture is concentrated
  5. dissolutionthe residue dissolved in Et2O (20 mL)
  6. washThe organic solution is washed with H2O (1×10 mL) and brine (1×20 mL)
  7. extractionThe aqueous layer is extracted with Et2O (3×10 mL)
  8. dry with materialthe combined extracts are dried (Na2SO4)
  9. concentrationconcentrated
  10. washChromatography (SiO2, 30–50% EtOAc-hexanes gradient elution)

Sources & evidence

ORD record
ord-bb7081ed2f814dd191d48403ab573187
Source dataset
uspto-grants-2007_03
Patent number
US07192980B2

Reaction notes

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