Sodium borohydride → HCID 66810576、化合物

HRID 1619900ノート

反応式

HRID 1619900 の反応式
[CH2:1]=[C:2]1[CH2:7][C:6]([N+:8]([O-:10])=[O:9])=[C:5]([C:11]2[CH:16]=[C:15]([F:17])[C:14]([F:18])=[CH:13][C:12]=2[F:19])[O:4][CH2:3]1.[BH4-].[Na+]>C(Cl)(Cl)Cl.C(O)(C)C>[CH2:1]=[C:2]1[CH2:3][O:4][C@@H:5]([C:11]2[CH:16]=[C:15]([F:17])[C:14]([F:18])=[CH:13][C:12]=2[F:19])[C@H:6]([N+:8]([O-:10])=[O:9])[CH2:7]1

参加物

5

反応物 2

HCID 4311764Sodium borohydrideHCID 57424364HCID 57424364、化合物

生成物 1

HCID 66810576HCID 66810576、化合物

試薬・触媒・溶媒 2

HCID 3776Isopropanol溶媒HCID 6212Chloroform溶媒

実験手順

To a solution of 3-methylene-5-nitro-6-(2,4,5-trifluorophenyl)-3,4-dihydro-2H-pyran (798 mg, 2.94 mmol) in chloroform (42 mL) and isopropyl alcohol (7.8 mL) was added silica gel (5.1 g), and sodium borohydride (420 mg, 11.1 mmol), and the reaction mixture stirred for 30 minutes at room temperature. The reaction mixture was then quenched by dropwise addition of hydrochloric acid (6 mL, 2N) and filtered. The resulting solid residue was washed with ethyl acetate (100 mL). The combined filtrate was washed successively with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous sodium sulfate, and evaporated. The resultant amber oil (802 mg) was dissolved in tetrahydrofuran (15 mL) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 40 μL) was added. The solution was stirred for 105 minutes and then transferred to a separatory funnel containing ethyl acetate (100 mL) and 1N hydrochloric acid (50 mL). The organic layer was washed with brine and the aqueous layer extracted with ethyl acetate. The combined organic layer was dried over anhydrous sodium sulfate, filtered and evaporated to yield a crude product which was purified by flash chromatography (silica, 8-10% ether in hexane) to yield trans-5-methylene-3-nitro-2-(2,4,5 trifluorophenyl)tetrahydro-2H-pyran. A portion of this product (388 mg) was resolved by HPLC (ChiralCel OD, 1.5% isopropyl alcohol in heptane) to yield the slower-moving enantiomer, (2R,3S)-5-methylene-3-nitro-2-(2,4,5-trifluorophenyl)tetrahydro-2H-pyran.

後処理

  1. customThe reaction mixture was then quenched by dropwise addition of hydrochloric acid (6 mL, 2N)
  2. filtrationfiltered
  3. washThe resulting solid residue was washed with ethyl acetate (100 mL)
  4. washThe combined filtrate was washed successively with saturated aqueous sodium bicarbonate solution and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated
  7. dissolutionThe resultant amber oil (802 mg) was dissolved in tetrahydrofuran (15 mL)
  8. addition1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 40 μL) was added
  9. stirringThe solution was stirred for 105 minutes
  10. customtransferred to a separatory funnel
  11. additioncontaining ethyl acetate (100 mL) and 1N hydrochloric acid (50 mL)
  12. washThe organic layer was washed with brine
  13. extractionthe aqueous layer extracted with ethyl acetate
  14. dry with materialThe combined organic layer was dried over anhydrous sodium sulfate
  15. filtrationfiltered
  16. customevaporated
  17. customto yield a crude product which
  18. customwas purified by flash chromatography (silica, 8-10% ether in hexane)

出典と根拠

ORDレコード
ord-efac3554287140519383c070f57c1976
出典データセット
uspto-grants-2014_07
特許番号
US08772328B2

反応ノート

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