Thiophenol → (R)-methyl 3-(benzyloxycarbonylamino)-4-(phenylthio)butanoate

HRID 1771161

反応式

HRID 1771161 の反応式
[C:1]1([SH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:8]([O:15][C:16]([NH:18][C@@H:19]([CH2:25]O)[CH2:20][C:21]([O:23][CH3:24])=[O:22])=[O:17])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C(P(CCCC)CCCC)CCC.N(/C(N1CCCCC1)=O)=N\C(N1CCCCC1)=O>C1COCC1>[CH2:8]([O:15][C:16]([NH:18][C@@H:19]([CH2:25][S:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH2:20][C:21]([O:23][CH3:24])=[O:22])=[O:17])[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

参加物

6

反応物 4

HCID 7969ThiophenolHCID 13831TributylphosphineHCID 5702657diazenedicarboxylic acid bis(N,N-piperidide)HCID 59108917Methyl (R)-3-[(benzyloxycarbonyl)amino]-4-hydroxybutanoate2 回

生成物 1

HCID 66723634(R)-methyl 3-(benzyloxycarbonylamino)-4-(phenylthio)butanoate収率 70.4%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of benzenethiol (11.16 ml, 108.65 mmol), (R)-methyl 3-(benzyloxycarbonylamino)-4-hydroxybutanoate (INTERMEDIATE 4, 26.4 g, 98.77 mmol) and tributylphosphine (34.5 ml, 138.28 mmol) in anhydrous THF (350 ml) under nitrogen atmosphere was added. A solution of (E)-diazene-1,2-diylbis(piperidin-1-ylmethanone) (34.9 g, 138.22 mmol) in anhydrous THF (350 ml) was added dropwise over a 30 minute period. During the addition a white precipitate was formed and stirring was continued for 2 hours after the addition was complete. The white precipitate was filtered off and evaporation of the volatiles under reduced pressure gave a residue, which was purified by column chromatography (ISCO, eluting with 0→100% EtOAc/hexanes) to give the title product (25.0 g, yield: 70%).

後処理

  1. additionDuring the addition a white precipitate
  2. customwas formed
  3. additionafter the addition
  4. filtrationThe white precipitate was filtered off
  5. customevaporation of the volatiles under reduced pressure
  6. customgave a residue, which
  7. customwas purified by column chromatography (ISCO, eluting with 0→100% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-70854a4df8004817a9dbb8969b39e22f
出典データセット
uspto-grants-2016_02
特許番号
US09248140B2

関連ノート

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