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

HRID 2306386
Notes
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Reaction equation

HRID 2306386 reaction equation
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
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 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

Product 1

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

Reagents, catalysts & solvents 3

HCID 23994ZincCatalyst6×HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 8028TetrahydrofuranSolvent5×

Conditions

Temperature
25 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-0dec5f65e9904a03af463d34d5561721
Source dataset
uspto-grants-2002_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06441180B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes