Pyridine → 5-bromopentyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-enyl carbonate

HRID 1269357Notes

Reaction equation

HRID 1269357 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][OH:7].N1C=CC=CC=1.ClC(Cl)(O[C:18](=[O:24])[O:19][C:20](Cl)(Cl)Cl)Cl.[Si:26]([O:33][CH2:34]/[C:35](/[C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)=[C:36](/[C:39]1[CH:44]=[CH:43][C:42]([S:45]([CH3:48])(=[O:47])=[O:46])=[CH:41][CH:40]=1)\CO)([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:28])[CH3:27].[Cl-].[NH4+]>C(Cl)Cl>[C:18](=[O:24])([O:19][CH2:20]/[C:36](/[C:39]1[CH:44]=[CH:43][C:42]([S:45]([CH3:48])(=[O:47])=[O:46])=[CH:41][CH:40]=1)=[C:35](/[C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)\[CH2:34][O:33][Si:26]([C:29]([CH3:32])([CH3:30])[CH3:31])([CH3:28])[CH3:27])[O:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][Br:1]

Participants

7

Reactant 5

HCID 1049Pyridine2×HCID 25517Ammonium ChlorideHCID 94429TriphosgeneHCID 1187091-Pentanol, 5-bromo-HCID 58787782(2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-ol

Product 1

HCID 588411855-bromopentyl (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-enyl carbonate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 5-bromo-1-pentanol (1 eq, 0.35M) in CH2Cl2 was added pyridine (1.1 eq). The mixture was cooled at −78° C. and a solution of triphosgene (0.33 eq, 0.1M) was slowly added, the mixture was warmed to rt and stirred for 5 min. The reaction mixture was then slowly added to a mixture of (2Z)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-ol (L eq) and pyridine (1 eq) in CH2Cl (0.35M) precooled at −78° C. The reaction mixture was warmed to 0° C. and stirred 5 min. Saturated aqueous ammonium chloride was added and the mixture was extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered and concentrated. The residue was purified by flash chromatography on silica gel eluted with 1:6 to 1:1 EtOAc/hexanes to give the titled compound.

Workup

  1. temperaturethe mixture was warmed to rt
  2. customprecooled at −78° C
  3. temperatureThe reaction mixture was warmed to 0° C.
  4. stirringstirred 5 min
  5. extractionthe mixture was extracted with EtOAc
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography on silica gel
  10. washeluted with 1:6 to 1:1 EtOAc/hexanes

Sources & evidence

ORD record
ord-a48737ac9e82473ba79e94eca16f836c
Source dataset
uspto-grants-2007_04
Patent number
US07199154B2

Reaction notes

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