Triphenylphosphine → N-(cyanomethyl)-3-{[(4-fluorophenyl)sulfanyl]methyl}bicyclo[2.2.1]hept-5-ene-2-carboxamide

HRID 2222913Notes

Reaction equation

HRID 2222913 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.[C:34]([CH2:36][NH:37][C:38]([CH:40]1[CH:45]([CH2:46]O)[CH:44]2[CH2:48][CH:41]1[CH:42]=[CH:43]2)=[O:39])#[N:35].[F:49][C:50]1[CH:55]=[CH:54][C:53]([SH:56])=[CH:52][CH:51]=1>CN(C)C=O>[C:34]([CH2:36][NH:37][C:38]([CH:40]1[CH:45]([CH2:46][S:56][C:53]2[CH:54]=[CH:55][C:50]([F:49])=[CH:51][CH:52]=2)[CH:44]2[CH2:48][CH:41]1[CH:42]=[CH:43]2)=[O:39])#[N:35]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 677894-FluorothiophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86596131N-(cyanomethyl)-3-(hydroxymethyl)bicyclo[2.2.1]hept-5-ene-2-carboxamide

Product 1

HCID 86596133N-(cyanomethyl)-3-{[(4-fluorophenyl)sulfanyl]methyl}bicyclo[2.2.1]hept-5-ene-2-carboxamide

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of triphenylphosphine (120 mg, 460 μmol) in dimethylformamide (1.0 mL) was cooled to 0° C. Diisopropyl azodicarboxylate (83 μL, 420 μmol) was added and the reaction mixture was stirred for 2 min. (1R/S,2R/S,3R/S,4S/R)-N-(cyanomethyl)-3-(hydroxymethyl)-bicyclo[2.2.1]hept-5-ene-2-carboxamide (79 mg, 380 μmol) and 4-fluorothiophenol (45 μl, 420 μmol) were added and the reaction mixture was stirred at ambient temperature for 2.5 h. The reaction mixture was partitioned between ethyl acetate (10 mL) and 1:1 water:saturated aqueous sodium chloride (10 mL). The product was extracted into ethyl acetate, dried with anhydrous sodium sulfate and concentrated. Chromatography of the residue on silica gel eluting with 4:96 methanol:dichloromethane provided (1R/S,2R/S,3R/S,4S/R)-N-(cyanomethyl)-3-{[(4-fluorophenyl)sulfanyl]methyl}bicyclo[2.2.1]hept-5-ene-2-carboxamide as a colorless syrup.

Workup

  1. additionwere added
  2. customThe reaction mixture was partitioned between ethyl acetate (10 mL) and 1:1 water
  3. extractionThe product was extracted into ethyl acetate
  4. dry with materialdried with anhydrous sodium sulfate
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-8f919523236f4ea9b7672f952d6380ec
Source dataset
uspto-grants-2008_05
Patent number
US07371747B2

Reaction notes

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