Triphenylphosphine → HCID 86596146, 화합물

HRID 2222929노트

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HRID 2222929 반응식
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

참가 물질

9

반응물 5

HCID 11776TriphenylphosphineHCID 677894-FluorothiophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86593035HCID 86593035, 화합물HCID 86596147HCID 86596147, 화합물

생성물 1

HCID 86596146HCID 86596146, 화합물

시약·촉매·용매 3

HCID 3283Diethyl Ether용매HCID 6228Dimethylformamide용매2회HCID 57417360Sodium chloride; water용매

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온도
0 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-5847444b7fc841cea31a77b0c481b000
출처 데이터셋
uspto-grants-2008_05
특허 번호
US07371747B2

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