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

HRID 2222914Notes

Reaction equation

HRID 2222914 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[CH2:42][CH2:43]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 86596135N-(cyanomethyl)-3-{[(4-fluorophenyl)sulfanyl]methyl}bicyclo[2.2.1]heptane-2-carboxamide

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of triphenylphosphine (140 mg, 540 mmol) in dimethylformamide (1.0 mL) was cooled to 0° C. Diisopropyl azodicarboxylate (98 μL, 500 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 (94 mg, 450 μmol) and 4-fluorothiophenol (53 μL, 500 μmol) were added. After stirring the reaction mixture for 19 h, it was partitioned between ethyl acetate (20 mL) and 1:1 water:saturated aqueous sodium chloride (20 mL). The product was extracted into ethyl acetate and the combined organics were washed with 1 mL saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and concentrated using a rotary evaporator. Chromatography of the residue on silica gel eluting with 1:2 ethyl acetate:hexanes provided (1S/R,2R/S,3R/S,4R/S)-N-(cyanomethyl)-3-{[(4-fluorophenyl)sulfanyl]methyl}bicyclo[2.2.1]heptane-2-carboxamide as a colorless syrup.

Workup

  1. additionwere added
  2. customit was partitioned between ethyl acetate (20 mL) and 1:1 water
  3. extractionThe product was extracted into ethyl acetate
  4. washthe combined organics were washed with 1 mL saturated aqueous sodium chloride solution
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customa rotary evaporator

Sources & evidence

ORD record
ord-306d78629b414a69b3bc2887db66edd2
Source dataset
uspto-grants-2008_05
Patent number
US07371747B2

Reaction notes

Loading…