Trichloroacetyl isocyanate → HCID 86760456, compound

HRID 459072Notes

Reaction equation

HRID 459072 reaction equation
[CH3:1][C:2]([Si:5]([CH3:50])([CH3:49])[O:6][C@H:7]([C@@H:22]([CH3:48])/[CH:23]=[C:24](/[CH3:47])\[CH2:25][C@H:26]([CH3:46])[C@@H:27]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])[C@H:28]([CH3:37])[C@@H:29]([OH:36])[C@@H:30]([CH3:35])/[CH:31]=[CH:32]\[CH:33]=[CH2:34])[C@@H:8]([CH3:21])[CH2:9][N:10]([CH3:20])[C:11](=[O:19])[CH2:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)([CH3:4])[CH3:3].ClC(Cl)(Cl)[C:53]([N:55]=C=O)=[O:54]>C(Cl)Cl>[NH2:55][C:53]([O:36][C@@H:29]([C@@H:30]([CH3:35])/[CH:31]=[CH:32]\[CH:33]=[CH2:34])[C@@H:28]([CH3:37])[C@H:27]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:40])[CH3:41])[C@@H:26]([CH3:46])[CH2:25]/[C:24](/[CH3:47])=[CH:23]\[C@H:22]([CH3:48])[C@@H:7]([O:6][Si:5]([C:2]([CH3:4])([CH3:3])[CH3:1])([CH3:49])[CH3:50])[C@@H:8]([CH3:21])[CH2:9][N:10]([CH3:20])[C:11](=[O:19])[CH2:12][CH:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)=[O:54]

Participants

4

Reactant 2

HCID 76400Trichloroacetyl isocyanateHCID 86760455HCID 86760455, compound

Product 1

HCID 86760456HCID 86760456, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
23 °C

Procedure

A solution of N-[(2S,3R,4S,5Z,8S,9R,10R,11S,12S,13Z)-3,9-bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]-11-hydroxy-2,4,6,8,10,12-hexamethyl-5,13,15-hexadecatrienyl]-N-methyl-cyclohexaneacetamide (70 mg, 0.096 mmol, 1 eq) in CH2Cl2 (2.0 mL) is treated with trichloroacetyl isocyanate (27.2 g, 0.145 mmol, 1.5 eq) at 23° C. (20 minutes). The solution is concentrated, and the residue dissolved in CH3OH (2.0 mL). To this solution is added K2CO3 (10 mg) and the mixture is stirred at 23° C. (2 hours). The reaction mixture is concentrated and the residue dissolved in Et2O (10 mL). The organic solution is filtered through Celite and concentrated. Chromatography (SiO2, 0–30% EtOAc-hexanes gradient elution) provided the desired compound (70 mg, 94%): HRMS ESI m/z 777.5984 (M+H+, C44H85O5N2Si2 requires 777.5997).

Workup

  1. concentrationThe solution is concentrated
  2. dissolutionthe residue dissolved in CH3OH (2.0 mL)
  3. additionTo this solution is added K2CO3 (10 mg)
  4. concentrationThe reaction mixture is concentrated
  5. dissolutionthe residue dissolved in Et2O (10 mL)
  6. filtrationThe organic solution is filtered through Celite
  7. concentrationconcentrated
  8. washChromatography (SiO2, 0–30% EtOAc-hexanes gradient elution)

Sources & evidence

ORD record
ord-e6a6151afe394534b978083649d9b6d9
Source dataset
uspto-grants-2007_03
Patent number
US07192980B2

Reaction notes

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