3-(Tert-butyl-diphenyl-silanyloxy)-5-hydroxy-2-trityloxymethyl-cyclopentanone → 4-(Tert-butyl-diphenyl-silanyloxy)-2-methylene-3-trityloxymethyl-cyclopentanol

HRID 1047102Notes

Reaction equation

HRID 1047102 reaction equation
Br[Zn]C[Zn]C[Zn]Br.[CH2:8]1OCCC1.[C:13]([Si:17]([C:53]1[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1)([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[O:18][CH:19]1[CH2:23][CH:22]([OH:24])[C:21](=O)[CH:20]1[CH2:26][O:27][C:28]([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([CH3:16])([CH3:15])[CH3:14]>O1CCCC1.Cl[Ti](Cl)(Cl)Cl>[C:13]([Si:17]([C:47]1[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=1)([C:53]1[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=1)[O:18][CH:19]1[CH2:23][CH:22]([OH:24])[C:21](=[CH2:8])[CH:20]1[CH2:26][O:27][C:28]([C:41]1[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=1)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)([CH3:14])([CH3:15])[CH3:16]

Participants

5

Reactant 2

HCID 674394363-(Tert-butyl-diphenyl-silanyloxy)-5-hydroxy-2-trityloxymethyl-cyclopentanoneHCID 178420636HCID 178420636, compound

Product 1

HCID 670851784-(Tert-butyl-diphenyl-silanyloxy)-2-methylene-3-trityloxymethyl-cyclopentanolYield 50%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

2.4 ml (1.26 mmol) of 20% suspension Nysted reagent and 6.4 ml of tetrahydrofuran were added dropwise to a reactor successively and cooled to 0° C. 0.14 ml (1.26 mmol) of TiCl4 was added thereto dropwise, and the resulting mixture was stirred. The reaction mixture was cooled to −40° C., and a solution which had been prepared by dissolving 0.527 g (0.842 mmol) of 3-(tert-butyl-diphenyl-silanyloxy)-5-hydroxy-2-trityloxymethyl-cyclopentanone (a compound of formula (2)) obtained in Example 2 in 2.4 ml of tetrahydrofuran was added thereto. The reaction mixture was stirred at room temperature for 3.5 hrs. After completion of the reaction, the reaction mixture was cooled to −20° C., quenched by adding 25 ml of 1N hydrochloric acid, and extracted with 25 ml of dichloromethane to separate an organic layer. The organic layer was washed with 20 ml of 4% sodium bicarbonate solution and 20 ml of brine successively, dried over anhydrous sodium sulfate, filtered, and condensed. The residue thus obtained was isolated by HPLC to obtain 0.184 g of the title compound (yield: 50%).

Workup

  1. temperatureThe reaction mixture was cooled to −40° C.
  2. customa solution which had been prepared
  3. additionwas added
  4. stirringThe reaction mixture was stirred at room temperature for 3.5 hrs
  5. customAfter completion of the reaction
  6. temperaturethe reaction mixture was cooled to −20° C.
  7. customquenched
  8. additionby adding 25 ml of 1N hydrochloric acid
  9. extractionextracted with 25 ml of dichloromethane
  10. customto separate an organic layer
  11. washThe organic layer was washed with 20 ml of 4% sodium bicarbonate solution and 20 ml of brine successively
  12. dry with materialdried over anhydrous sodium sulfate
  13. filtrationfiltered
  14. customcondensed
  15. customThe residue thus obtained
  16. customwas isolated by HPLC

Sources & evidence

ORD record
ord-48c0969a3afe4305a96dc2ab8c95a83d
Source dataset
uspto-grants-2013_10
Patent number
US08569490B2

Reaction notes

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