Triphenylphosphine → HCID 86596146、化合物

HRID 2222929ノート

反応式

HRID 2222929 の反応式
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

参加物

9

反応物 5

HCID 11776TriphenylphosphineHCID 677894-FluorothiophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86593035HCID 86593035、化合物HCID 86596147HCID 86596147、化合物

生成物 1

HCID 86596146HCID 86596146、化合物

試薬・触媒・溶媒 3

HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒2 回HCID 57417360Sodium chloride; water溶媒

反応条件

温度
0 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-5847444b7fc841cea31a77b0c481b000
出典データセット
uspto-grants-2008_05
特許番号
US07371747B2

反応ノート

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