Hexane → (3R, 4R)-2-methylene-3-[(1E,3S)-3-(tert-butyldimethylsiloxy)-3-cyclohexyl-1-propenyl]-4-(tert-butyldimethylsiloxy)cyclopentan-1-one

HRID 1583101Notes

Reaction equation

HRID 1583101 reaction equation
I/[CH:2]=[CH:3]/[C@@H:4]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[CH:5]1[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1.C([Li])(C)(C)C.C(N([CH2:29][C:30]1[C:31](=[O:43])[CH2:32][C@@H:33]([O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[CH:34]=1)CC)C.CCCCCC>CCOCC>[CH2:29]=[C:30]1[C@@H:34](/[CH:2]=[CH:3]/[C@@H:4]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[CH:5]2[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]2)[C@H:33]([O:35][Si:36]([C:39]([CH3:41])([CH3:40])[CH3:42])([CH3:37])[CH3:38])[CH2:32][C:31]1=[O:43]

Participants

6

Reactant 4

HCID 8058HexaneHCID 10424731(4R)-2-(N,N-diethylamino)methyl-4-(tert-butyldimethylsiloxy)cyclopent-2-en-1-oneHCID 10904993(1E,3S)-1-Iodo-3-(tert-butyldimethylsiloxy)-3-cyclohexyl-1-propeneHCID 178418306HCID 178418306, compound

Product 1

HCID 11733520(3R, 4R)-2-methylene-3-[(1E,3S)-3-(tert-butyldimethylsiloxy)-3-cyclohexyl-1-propenyl]-4-(tert-butyldimethylsiloxy)cyclopentan-1-one

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

(1E,3S)-1-Iodo-3-(tert-butyldimethylsiloxy)-3-cyclohexyl-1-propene (2.66 g) was dissolved in ether (28 ml), tert-butyl lithium (1.7 M, pentane solution, 8.24 ml) was added at −78° C. After stirring at the same temperature for an hour, lithium 2-thienylcyanocuprate (0.25 M, tetrahydrofuran solution, 39.2 ml) was added, followed by stirring at the same temperature for 20 minutes, and (4R)-2-(N,N-diethylamino)methyl-4-(tert-butyldimethylsiloxy)cyclopent-2-en-1-one (0.25 M, ether solution, 28 ml) was added. The temperature was raised to 0° C. with stirring over 1.5 hours. To the reaction solution were added hexane (70 ml) and a saturated aqueous ammonium chloride solution (105 ml) and, after extraction with hexane, the extract was washed with a saturated aqueous sodium chloride solution, dried, concentrated and purified by a silica gel column chromatography (developing solvent; n-hexane:ethyl acetate=30:1) to give (3R, 4R)-2-methylene-3-[(1E,3S)-3-(tert-butyldimethylsiloxy)-3-cyclohexyl-1-propenyl]-4-(tert-butyldimethylsiloxy)cyclopentan-1-one (910 mg).

Workup

  1. stirringby stirring at the same temperature for 20 minutes
  2. stirringwith stirring over 1.5 hours
  3. extractiona saturated aqueous ammonium chloride solution (105 ml) and, after extraction with hexane
  4. washthe extract was washed with a saturated aqueous sodium chloride solution
  5. customdried
  6. concentrationconcentrated
  7. custompurified by a silica gel column chromatography (developing solvent; n-hexane:ethyl acetate=30:1)

Sources & evidence

ORD record
ord-ce8e6c2cffa041e998cc58b1c9ded951
Source dataset
uspto-grants-2004_05
Patent number
US06740772B1

Reaction notes

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