Triphenylphosphine → HCID 86596146, compound

HRID 2222929Notes

Reaction equation

HRID 2222929 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.O[CH2:35][CH:36]1[CH2:41][CH2:40][CH:39]([CH3:42])[CH2:38][CH:37]1[C:43]([O:45][CH2:46][CH3:47])=[O:44].[F:48][C:49]1[CH:54]=[CH:53][C:52]([SH:55])=[CH:51][CH:50]=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C)C=O.[Cl-].[Na+].O.CCOCC>[F:48][C:49]1[CH:54]=[CH:53][C:52]([S:55][CH2:35][CH:36]2[CH2:41][CH2:40][CH:39]([CH3:42])[CH2:38][CH:37]2[C:43]([O:45][CH2:46][CH3:47])=[O:44])=[CH:51][CH:50]=1

Participants

9

Reactant 5

HCID 11776TriphenylphosphineHCID 677894-FluorothiophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86593035HCID 86593035, compoundHCID 86596147HCID 86596147, compound

Product 1

HCID 86596146HCID 86596146, compound

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
0 °C

Procedure

To a cold (0° C.) solution of triphenylphosphine (260 mg, 1.0 mmol) in dimethylformamide (1 mL) was added diisopropyl azodicarboxylate (180 μL, 0.9 mmol) and the reaction mixture was stirred at 0° C. for 10 min. A mixture of (1R/S,3R/S,6R/S)-ethyl 2-(hydroxymethyl)-5-methylcyclohexanecarboxylate and (1R/S,3S/R,6R/S)-ethyl 2-(hydroxymethyl)-5-methylcyclohexanecarboxylate (1:1 mixture, 160 mg, 0.8 mmol) and 4-fluorobenzenethiol (100 μL, 0.9 mmol) in dimethylformamide (1 mL) was added to the diisopropyl azodicarboxylate/triphenylphosphine mixture. The reaction mixture was warmed to room temperature and stirred for 3 h. Ether and brine were added and the aqueous layer was extracted with ether. The combined organic extracts were concentrated in vacuo and the residue was purified by flash chromatography over silica gel (ether/hexanes, 5/95) to afford the product (1R/S,3R/S,6R/S)-ethyl 2-{[(4-fluorophenyl)sulfanyl]methyl}-5-methylcyclohexanecarboxylate and (1R/S,3S/R,6R/S)-ethyl 2-{[(4-fluorophenyl)sulfanyl]methyl}-5-methylcyclohexane-carboxylate as a 1:1 mixture of diastereomers.

Workup

  1. temperatureThe reaction mixture was warmed to room temperature
  2. stirringstirred for 3 h
  3. extractionthe aqueous layer was extracted with ether
  4. concentrationThe combined organic extracts were concentrated in vacuo
  5. customthe residue was purified by flash chromatography over silica gel (ether/hexanes, 5/95)

Sources & evidence

ORD record
ord-5847444b7fc841cea31a77b0c481b000
Source dataset
uspto-grants-2008_05
Patent number
US07371747B2

Reaction notes

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