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Triethylamine → (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

HRID 2194649
ノート
印刷プレビュー

反応式

HRID 2194649 の反応式
[C:1]([O:4][C@H:5]1[C@H:10]([NH2:11])[C@@H:9]([O:12][C:13](=[O:15])[CH3:14])[C@H:8]([O:16][C:17](=[O:19])[CH3:18])[C@@H:7]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[O:6]1)(=[O:3])[CH3:2].[CH:25]1[C:37]2[CH:36]([CH2:38][O:39][C:40]([N:42]=[C:43]=[S:44])=[O:41])[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[C:29]=2[CH:28]=[CH:27][CH:26]=1.C(N(CC)CC)C>N1C=CC=CC=1>[C:1]([O:4][C@H:5]1[C@H:10]([NH:11][C:43]([NH:42][C:40]([O:39][CH2:38][CH:36]2[C:35]3[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=3[C:29]3[C:37]2=[CH:25][CH:26]=[CH:27][CH:28]=3)=[O:41])=[S:44])[C@@H:9]([O:12][C:13](=[O:15])[CH3:14])[C@H:8]([O:16][C:17](=[O:19])[CH3:18])[C@@H:7]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[O:6]1)(=[O:3])[CH3:2]
参加物実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 8471TriethylamineHCID 202260[(2R,3S,4R,5R,6S)-3,4,6-triacetyloxy-5-aminooxan-2-yl]methyl acetateHCID 4154759Fmoc isothiocyanate

生成物 1

HCID 86638169(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate収率 89%

試薬・触媒・溶媒 1

HCID 1049
Pyridine
溶媒

実験手順

The amine from above (220 mg) was dissolved in pyridine (5 mL) and 9-Fluorenylmethoxycarbonyl isothiocyanate (180 mg, 0.65 mmol) and triethylamine (0.02 mL) was added. Then the resulting mixture was stirred at room temperature for 16 h. The solution was concentrated and the residue taken up in CH2Cl2 (20 mL) and diluted with saturated aqueous NaHCO3 (20 mL), then the resulting mixture was extracted with CH2Cl2 (3×10 mL) and the combined organic extracts were dried (Na2SO4) and concentrated. Flash chromatography of the residue (EtOAc:hexanes 2:3) gave (2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate as a white foam (360 mg, 89% yield over two steps). 1H NMR (600 MHz, CDCl3) δ 2.06 (s, 3H), 2.07 (s, 3H), 2.12 (s, 3H), 2.14 (s, 3H), 3.89 (ddd, 1H, J=2.4, 4.8, 9.6 Hz), 4.17 (dd, 1H, J=2.4, 12.5 Hz), 4.24 (dd, 1H, J=6.6, 6.6 Hz), 4.33 (dd, 1H, J=4.8, 12.5 Hz), 4.52 (s, 1H), 4.54 (s, 1H), 5.08-5.12 (m, 1H), 5.22 (dd, 1H, J=9.5, 9.6 Hz), 5.34 (dd, 1H, J=6.6, 9.5 Hz), 5.88 (d, 1H, J=6.6 Hz), 7.36 (dd, 2H, J=7.2, 7.8 Hz), 7.45 (dd, 2H, J=7.2, 7.8 Hz), 7.57 (d, 2H, J=7.8 Hz), 7.80 (d, 2H, J=7.2 Hz). 13C NMR (150 MHz, CDCl3) δ 20.62, 20.72, 20.77, 21.05, 46.49, 57.59, 61.65, 67.47, 68.40, 72.21, 72.87, 92.21, 120.09, 120.29, 124.84, 124.96, 125.32, 127.30, 127.83, 128.15, 128.25, 129.06, 141.37, 142.80, 152.16, 169.27, 169.34, 170.46, 170.72, 180.22.

後処理

  1. concentrationThe solution was concentrated
  2. additiondiluted with saturated aqueous NaHCO3 (20 mL)
  3. extractionthe resulting mixture was extracted with CH2Cl2 (3×10 mL)
  4. dry with materialthe combined organic extracts were dried (Na2SO4)
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-a47ec64919f9466fa653ee7a5559ada8
出典データセット
uspto-grants-2012_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08334310B2

反応ノート

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