Water → Hexaethyldisiloxane

HRID 890615Notes

Reaction equation

HRID 890615 reaction equation
CC[C@@H]1NC(=O)[C@H]([C@H](O)[C@@H](C/C=C/C)C)N(C)C(=O)[C@H](C(C)C)N(C)C(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](CC(C)C)N(C)C(=O)[C@@H](C)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](C(C)C)NC(=O)[C@H](C[CH:81]([CH3:83])C)N(C)C(=O)CN(C)C1=O.FC(F)(F)S([O:91][Si:92]([CH2:97][CH3:98])([CH2:95][CH3:96])[CH2:93][CH3:94])(=O)=O.O>N1C=CC=CC=1.CN(C1C=CN=CC=1)C>[CH2:93]([Si:92]([O:91][Si:92]([CH2:81][CH3:83])([CH2:95][CH3:96])[CH2:93][CH3:94])([CH2:97][CH3:98])[CH2:95][CH3:96])[CH3:94]

Participants

6

Reactant 3

HCID 962WaterHCID 2733308Triethylsilyl trifluoromethanesulphonateHCID 5284373Cyclosporin A

Product 1

HCID 70442Hexaethyldisiloxane

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Conditions

Temperature
0 °C

Procedure

Cyclosporin A (3.606 g, 3 mmol) was dissolved in dry pyridine (8 mL) and then DMAP (122 mg, 1 mmol) was added. The reaction mixture was cooled to 0° C. and then triethylsilyl trifluoromethanesulfonate (3.6 mmol) added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was then poured slowly into water with stirring. The precipitated triethylsilyl ether was filtered off and washed with water. The collected cake was dissolved in a minimum volume of methanol and added to a 5% citric acid solution and stirred for 30 minutes. The precipitated product was collected by filtration and washed with water until the pH of the filtrate reached that of the water. The solid triethylsilyl ether was dried at 50° C. under vacuum to give a colorless solid. Triisopropylsilyl and tert-butyldimethylsilyl protecting groups were also introduced by following an analogous procedure.

Workup

  1. temperatureto warm to room temperature
  2. stirringwith stirring
  3. filtrationThe precipitated triethylsilyl ether was filtered off
  4. washwashed with water
  5. dissolutionThe collected cake was dissolved in a minimum volume of methanol
  6. additionadded to a 5% citric acid solution
  7. stirringstirred for 30 minutes
  8. filtrationThe precipitated product was collected by filtration
  9. washwashed with water until the pH of the filtrate
  10. dry with materialThe solid triethylsilyl ether was dried at 50° C. under vacuum
  11. customto give a colorless solid
  12. additionTriisopropylsilyl and tert-butyldimethylsilyl protecting groups were also introduced

Sources & evidence

ORD record
ord-0e5eb25b6d804d4ba1b90f7cfaaa05f8
Source dataset
uspto-grants-2006_02
Patent number
US06998385B2

Reaction notes

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