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

HRID 1583101ノート

反応式

HRID 1583101 の反応式
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]

参加物

6

反応物 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、化合物

生成物 1

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

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
0 °C

実験手順

(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).

後処理

  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)

出典と根拠

ORDレコード
ord-ce8e6c2cffa041e998cc58b1c9ded951
出典データセット
uspto-grants-2004_05
特許番号
US06740772B1

反応ノート

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