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Chlorotrimethylsilane → (E)-3-cyclopentyl-2-[4-methanesulfonyl-3-(5-methyl-tetrazol-1-yl)-phenyl]-acrylic acid methyl ester

HRID 1936369
ノート
印刷プレビュー

反応式

HRID 1936369 の反応式
BrCCBr.C[Si](Cl)(C)C.[CH3:10][O:11][C:12](=[O:21])/[C:13](/I)=[CH:14]\[CH:15]1[CH2:19][CH2:18][CH2:17][CH2:16]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:42]1[CH:43]=[CH:44][C:45]([S:54]([CH3:57])(=[O:56])=[O:55])=[C:46]([N:48]2[C:52]([CH3:53])=[N:51][N:50]=[N:49]2)[CH:47]=1.[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:21])/[C:13](/[C:42]1[CH:43]=[CH:44][C:45]([S:54]([CH3:57])(=[O:56])=[O:55])=[C:46]([N:48]2[C:52]([CH3:53])=[N:51][N:50]=[N:49]2)[CH:47]=1)=[CH:14]/[CH:15]1[CH2:19][CH2:18][CH2:17][CH2:16]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 184343641-(5-bromo-2-methanesulfonyl-phenyl)-5-methyl-1H-tetrazoleHCID 86584747(E)-3-cyclopentyl-2-iodo-acrylic acid methyl ester

生成物 1

HCID 69691463
(E)-3-cyclopentyl-2-[4-methanesulfonyl-3-(5-methyl-tetrazol-1-yl)-phenyl]-acrylic acid methyl ester
収率 91%

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 (330 mg, 5 mmol, Aldrich, −325 mesh) and dry tetrahydrofuran (1 mL) under argon was treated with 1,2-dibromoethane (93 mg, 0.5 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 (54 mg, 0.5 mmol), and the suspension was stirred for 15 min at 25° C. The reaction mixture was then treated dropwise with a solution of (E)-3-cyclopentyl-2-iodo-acrylic acid methyl ester (prepared in Example 7, 420 mg, 1.5 mmol) in dry tetrahydrofuran (1 mL). The resulting reaction mixture was then stirred at 40-45° C. for 1 h and then stirred overnight at 25° C. The reaction mixture was then diluted with dry tetrahydrofuran (3 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) (27 mg, 0.05 mmol) and triphenylphosphine (52 mg, 0.2 mmol) in dry tetrahydrofuran (3 mL) was stirred at 25° C. under argon for 10 min and then treated with 1-(5-bromo-2-methanesulfonyl-phenyl)-5-methyl-1H-tetrazole (237 mg, 0.75 mmol) and the freshly prepared zinc compound in tetrahydrofuran. The resulting brick red solution was heated at 40-45° C. over the weekend. The reaction mixture was cooled to 25° C. and then poured into a saturated aqueous ammonium chloride solution (30 mL), and the organic compound was extracted into ethyl acetate (3×30 mL). The combined organic 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 40S, Silica, 3/1 to 1/1 hexanes/ethyl acetate) afforded (E)-3-cyclopentyl-2-[4-methanesulfonyl-3-(5-methyl-tetrazol-1-yl)-phenyl]-acrylic acid methyl ester (266 mg, 91%) as a white solid: mp 164-166° C.; EI-HRMS m/e calcd for C18H22N4O4S (M+) 390.1362, found 390.1368.

後処理

  1. temperatureto cool
  2. temperatureheated again
  3. customThe resulting reaction mixture
  4. stirringwas then stirred at 40-45° C. for 1 h
  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 40-45° C. over the weekend
  9. temperatureThe reaction mixture was cooled to 25° C.
  10. extractionthe organic compound was extracted into ethyl acetate (3×30 mL)
  11. washThe combined organic 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-f9ebef4fd0b34f16bf16ee9b539f0667
出典データセット
uspto-grants-2002_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06388088B1

反応ノート

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