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Chlorotrimethylsilane → (E)-4-cyclopentyl-2-(4-methanesulfonyl-phenyl)-but-2-enoic acid methyl ester

HRID 276223
ノート
印刷プレビュー

反応式

HRID 276223 の反応式
BrCCBr.C[Si](Cl)(C)C.[CH3:10][O:11][C:12](=[O:22])/[C:13](/I)=[CH:14]\[CH2:15][CH:16]1[CH2:20][CH2:19][CH2:18][CH2:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:42][S:43]([C:46]1[CH:51]=[CH:50][C:49](Br)=[CH:48][CH:47]=1)(=[O:45])=[O:44].[Cl-].[NH4+]>O1CCCC1.[Zn].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[CH3:10][O:11][C:12](=[O:22])/[C:13](/[C:49]1[CH:50]=[CH:51][C:46]([S:43]([CH3:42])(=[O:45])=[O:44])=[CH:47][CH:48]=1)=[CH:14]/[CH2:15][CH:16]1[CH2:20][CH2:19][CH2:18][CH2:17]1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

10

反応物 6

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 770141-Bromo-4-(methylsulphonyl)benzeneHCID 86584748(E)-4-cyclopentyl-2-iodo-but-2-enoic acid methyl ester

生成物 1

HCID 67483022
(E)-4-cyclopentyl-2-(4-methanesulfonyl-phenyl)-but-2-enoic acid methyl ester
収率 86%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒6 回HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium触媒HCID 8028Tetrahydrofuran溶媒5 回

反応条件

温度
25 °C

実験手順

A mixture of zinc dust (0.98 g, 15 mmol, Aldrich, −325 mesh) and dry tetrahydrofuran (3 mL) under argon was treated with 1,2-dibromoethane (0.14 g, 0.75 mmol). The zinc suspension was then heated with a heat gun to ebullition, allowed to cool, and heated again. This process was repeated three times to make sure the zinc dust was activated. The activated zinc dust suspension was then treated with trimethylsilyl chloride (82 mg, 0.75 mmol), and the suspension was stirred for 15 min at 25° C. The reaction mixture was then treated dropwise with a solution of (E)-4-cyclopentyl-2-iodo-but-2-enoic acid methyl ester (1.47 g, 5 mmol) in dry tetrahydrofuran (1.5 mL) over 3 min. After the addition, the reaction mixture was stirred for 1 h at 40-45° C. and then stirred overnight at 25° C. The reaction mixture was then diluted with dry tetrahydrofuran (5 mL), and the stirring was stopped to allow the excess zinc dust to settle down (˜2 h). In a separate reaction flask, bis(dibenzylideneacetone)palladium(0) (54 mg, 0.1 mmol) and triphenylphosphine (104 mg, 0.4 mmol) in dry tetrahydrofuran (10 mL) was stirred at 25° C. under argon for 10 min and then treated with 4-bromophenyl methyl sulfone (0.94 g, 4 mmol) and the freshly prepared zinc compound in tetrahydrofuran. The resulting brick red solution was heated at 50° C. for 24 h, at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was cooled to 25° C. and then poured into a saturated aqueous ammonium chloride solution (75 mL), and the organic compound was extracted into diethyl ether (3×50 mL). The combined ether extracts were washed with a saturated aqueous sodium chloride solution (1×100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40M, Silica, 3/7 hexanes/diethyl ether) afforded (E)-4-cyclopentyl-2-(4-methanesulfonyl-phenyl)-but-2-enoic acid methyl ester (1.10 g, 86%) as a colorless oil: EI-HRMS m/e calcd for C17H22O4S (M+) 322.1235, found 322.1239.

後処理

  1. temperatureto cool
  2. temperatureheated again
  3. additionAfter the addition
  4. stirringthe reaction mixture was stirred for 1 h at 40-45° C.
  5. stirringstirred overnight at 25° C
  6. custom(˜2 h)
  7. stirringwas stirred at 25° C. under argon for 10 min
  8. temperatureThe resulting brick red solution was heated at 50° C. for 24 h, at which time, thin layer chromatography analysis of the reaction mixture
  9. temperatureThe reaction mixture was cooled to 25° C.
  10. extractionthe organic compound was extracted into diethyl ether (3×50 mL)
  11. washThe combined ether extracts were washed with a saturated aqueous sodium chloride solution (1×100 mL)
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-8a1336bbefc942a0b03f0ea57331db7f
出典データセット
uspto-grants-2002_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06353111B1

反応ノート

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