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Tin tetrachloride → (3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate

HRID 1854238
ノート
印刷プレビュー

反応式

HRID 1854238 の反応式
C(O[C@H:5]1[C@H:10]([NH:11][C:12]([NH:14][C:15]([O:17][CH2:18][CH:19]2[C:31]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[C:25]3[C:20]2=[CH:21][CH:22]=[CH:23][CH:24]=3)=[O:16])=[S:13])[C@@H:9]([O:32][C:33](=[O:35])[CH3:34])[C@H:8]([O:36][C:37](=[O:39])[CH3:38])[C@@H:7]([CH2:40][O:41][C:42](=[O:44])[CH3:43])[O:6]1)(=O)C.Cl[Sn](Cl)(Cl)Cl.C([O-])(O)=O.[Na+]>C(Cl)Cl>[C:37]([O:36][C@@H:8]1[C@@H:7]([CH2:40][O:41][C:42](=[O:44])[CH3:43])[O:6][C@H:5]2[C@H:10]([N:11]=[C:12]([NH:14][C:15]([O:17][CH2:18][CH:19]3[C:31]4[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=4[C:25]4[C:20]3=[CH:21][CH:22]=[CH:23][CH:24]=4)=[O:16])[S:13]2)[C@H:9]1[O:32][C:33](=[O:35])[CH3:34])(=[O:39])[CH3:38]
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 24287Tin tetrachlorideHCID 516892Sodium BicarbonateHCID 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

生成物 1

HCID 86638170(3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate収率 69%

試薬・触媒・溶媒

1
HCID 6344Dichloromethane溶媒

実験手順

The thiourea from above (200 mg, 0.32 mmol) was dissolved in CH2Cl2 (4 mL) and SnCl4 (0.5 mL, 4.0 mmol) was added. Then the resulting mixture was stirred at room temperature for 16 h. The solution was diluted 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 (3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate as a pale colourless foam (125 mg, 69% yield). 1H NMR 500 MHz, CDCl3) δ 1.88 (s, 3H), 2.04 (s, 3H), 2.12 (s, 3H), 3.69 (m, 1H), 3.81 (ddd, 1H, J=2.5, 5.5, 6.5 Hz), 4.12 (dd, 1H, J=2.5, 12.5 Hz), 4.21-4.26 (m, 2H), 4.55 (dd, 1H, J=6.0, 12.5 Hz), 4.72-4.75 (dd, 1H, J=6.5, 6.5 Hz), 4.95 (dd, 1H J=5.5, 9.5 Hz), 5.24 (dd, 1H J=6.5, 9.5 Hz), 6.01 (d, 1H, J=6.5 Hz), 7.35 (dd, 2H, J=7.1, 7.8 Hz), 7.44 (dd, 2H, J=7.0, 7.8 Hz), 7.59 (d, 2H, J=7.1 Hz), 7.81 (d, 2H, J=7.0 Hz). 13C NMR (125 MHz, CDCl3) δ 20.62, 20.71, 21.35, 46.78, 57.91, 63.70, 67.92, 69.46, 71.88, 72.52, 90.23, 120.71, 120.89, 123.83, 124.04, 125.15, 127.76, 127.97, 129.61, 129.72, 130.08, 141.31, 142.86, 152.11, 161.43, 169.11, 169.63, 170.23.

後処理

  1. extractionthe resulting mixture was extracted with CH2Cl2 (3×10 mL)
  2. dry with materialthe combined organic extracts were dried (Na2SO4)
  3. concentrationconcentrated

出典と根拠

ORDレコード
ord-e37196565d824955b5e1931d042514c4
出典データセット
uspto-grants-2015_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08962664B2

反応ノート

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このページの内容参加物実験手順後処理出典と根拠反応ノート