Triphenylphosphine → (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(N-sulfamoyl-N-allyloxycarbonylamino)methylpyrrolidine

HRID 1034530ノート

反応式

HRID 1034530 の反応式
[C:1]([S:4][C@@H:5]1[CH2:9][N:8]([C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])[C@H:7]([CH2:16]O)[CH2:6]1)(=[O:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:37]([O:40][C:41]([NH:43][S:44]([NH2:47])(=[O:46])=[O:45])=[O:42])[CH:38]=[CH2:39].C(OC(N=NC(OCC)=O)=O)C>C(OCC)(=O)C.C1(C)C=CC=CC=1>[C:1]([S:4][C@@H:5]1[CH2:9][N:8]([C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])[C@H:7]([CH2:16][N:43]([S:44](=[O:45])(=[O:46])[NH2:47])[C:41]([O:40][CH2:37][CH:38]=[CH2:39])=[O:42])[CH2:6]1)(=[O:3])[CH3:2]

参加物

7

反応物 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 19605053Allyl sulfamoylcarbamateHCID 228426921-Pyrrolidinecarboxylic acid, 4-(acetylthio)-2-(hydroxymethyl)-, 2-propen-1-yl ester, (2S,4S)-

生成物 1

HCID 57143963(2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(N-sulfamoyl-N-allyloxycarbonylamino)methylpyrrolidine収率 100.6%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of (2S,4S)-4-acetylthio-1-allyloxycarbonylpyrrolidine-2-methanol (8.02 g: ca. 30 mmole) in ethyl acetate (83 ml) under ice cooling, triphenylphosphine (9.44 g: 13.6 mmole), N-allyloxycarbonylsulfamide (3.12 g: 15.9 mmole), and azodicarboxylic acid diethylester (5.67 ml: 36 mmole) are successively added. The mixture is stirred under ice cooling for 55 minutes and at room temperature for 4 hours. The reaction mixture is dissolved in toluene (60 ml), concentrated, diluted with toluene (60 ml), filtered to remove separating crystals, and the filtrate is concentrated. The residue is purified by silica gel chromatography to give (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(N-sulfamoyl-N-allyloxycarbonylamino)methylpyrrolidine (6.74 g). Yield: 55%. Colorless oil. NMR δ(CDCl3) ppm: 1.5 to 1.7(m, 1H), 2.35(s, 3H), 2.5 to 2.7(m, 1H), 3.19 (dd, J=6.3 Hz, J=11.5 Hz, 1H), 3.68 (dd, J=3.8 Hz, J=14.5 Hz, 1H), 3.9 to 4.3(m, 3H), 4.3 to 4.7(m, 5H), 5.2 to 5.4(m, 4H), 5.8 to 6.1(m, 4H).

後処理

  1. concentrationconcentrated
  2. additiondiluted with toluene (60 ml)
  3. filtrationfiltered
  4. customto remove
  5. customseparating crystals
  6. concentrationthe filtrate is concentrated
  7. customThe residue is purified by silica gel chromatography

出典と根拠

ORDレコード
ord-1a1626cfe05a4db2a7850ae2a9217987
出典データセット
uspto-grants-1994_05
特許番号
US05317016

反応ノート

読み込み中…