Dichloromethane → HCID 131736645、化合物

HRID 1481622ノート

反応式

HRID 1481622 の反応式
[Si:1]([O:8][C@@H:9]1[C@@H:17]([CH2:18][OH:19])[O:16][C@H:15]2[C@H:11]([N:12]=[C:13]([N:20]([CH2:28][CH3:29])[C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[S:14]2)[C@@H:10]1[F:30])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:31](Cl)Cl>C1COCC1>[Si:1]([O:8][C@@H:9]1[C@@H:17]([C@@H:18]([OH:19])[CH3:31])[O:16][C@H:15]2[C@H:11]([N:12]=[C:13]([N:20]([CH2:28][CH3:29])[C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[S:14]2)[C@@H:10]1[F:30])([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:2])[CH3:3]

参加物

4

反応物 2

HCID 6344DichloromethaneHCID 123998680HCID 123998680、化合物

生成物 1

HCID 131736645HCID 131736645、化合物

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of tert-butyl (3aR,5R,6R,7S,7aR)-6-(tert-butyldimethylsilyloxy)-7-fluoro-5-(hydroxymethyl)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazol-2-yl(ethyl)carbamate (600 mg, 1.3 mmol) in DCM (30 mL) was added DMP (806 mg, 1.9 mmol) at 0° C. After stirring at room temperature for 2 h, the reaction was quenched with mixed saturated aqueous NaHCO3 (20 mL) and Na2S2O3 (20 mL). The resulting solution was extracted with DCM (3×30 mL). The combined organic layer was dried over anhydrous Na2SO4 and concentrated under vacuum to give the crude aldehyde. The aldehyde was dissolved in THF (30 mL), treated with MeMgC1 (3 M in THF, 1.1 mL, 3.3 mmol) at 0° C.˜25° C. for 3 h. The reaction was then quenched with H2O (50 mL) and extracted with EtOAc (3×40 mL). The combined organic layer was dried over anhydrous Na2SO4 and concentrated under vacuum. The residue was purified by a silica gel column, eluted with 3%-30% EtOAc in petroleum ether to give tert-butyl (3aR,5R,6R,7S,7aR)-6-(tert-butyldimethylsilyloxy)-7-fluoro-5-((S)-1-hydroxyethyl)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazol-2-yl(ethyl)carbamate as a yellow oil (355 mg, 57% of 2 steps). (ES, m/z) [M+H]+ 479.0; 1H NMR (300 MHz, CDCl3) δ 6.20-6.14 (m, 1H), 4.95-4.65 (m, 1H), 4.44-4.25 (m, 2H), 4.08-3.79 (m, 4H), 1.51 (s, 9H), 1.25-1.14 (m, 6H), 0.87 (s, 9H), 0.12-0.06 (m, 6H).

後処理

  1. customthe reaction was quenched with mixed saturated aqueous NaHCO3 (20 mL) and Na2S2O3 (20 mL)
  2. extractionThe resulting solution was extracted with DCM (3×30 mL)
  3. dry with materialThe combined organic layer was dried over anhydrous Na2SO4
  4. concentrationconcentrated under vacuum
  5. customto give the crude aldehyde
  6. customThe reaction was then quenched with H2O (50 mL)
  7. extractionextracted with EtOAc (3×40 mL)
  8. dry with materialThe combined organic layer was dried over anhydrous Na2SO4
  9. concentrationconcentrated under vacuum
  10. customThe residue was purified by a silica gel column
  11. washeluted with 3%-30% EtOAc in petroleum ether

出典と根拠

ORDレコード
ord-b19d162f01994ea08a012f6c8d571c54
出典データセット
uspto-grants-2016_08
特許番号
US09409924B2

反応ノート

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