17beta-Methoxy-5beta-androstan-3-one → 3alpha-Hydroxy-17beta-methoxy-5beta-androstane

HRID 582509ノート

反応式

HRID 582509 の反応式
[CH3:1][O:2][C@H:3]1[CH2:8][CH2:7][C@H:6]2[C@H:9]3[C@H:19]([CH2:20][CH2:21][C@:4]12[CH3:5])[C@:17]1([CH3:18])[C@@H:12]([CH2:13][C:14](=[O:22])[CH2:15][CH2:16]1)[CH2:11][CH2:10]3.[H-].C(O[Al](OC(C)(C)C)OC(C)(C)C)(C)(C)C.[Li+]>C1COCC1.C(Cl)Cl>[OH:22][C@@H:14]1[CH2:15][CH2:16][C@@:17]2([CH3:18])[C@H:12]([CH2:11][CH2:10][C@@H:9]3[C@@H:19]2[CH2:20][CH2:21][C@@:4]2([CH3:5])[C@H:6]3[CH2:7][CH2:8][C@@H:3]2[O:2][CH3:1])[CH2:13]1

参加物

5

反応物 2

HCID 1493938617beta-Methoxy-5beta-androstan-3-oneHCID 16710494Lithium tri-tert-butoxyaluminohydride

生成物 1

HCID 128368633alpha-Hydroxy-17beta-methoxy-5beta-androstane収率 83.1%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-75 °C

実験手順

A solution of 17β-methoxy-5β-androstan-3-one (130 mg, 0.42 mmol) in dry THF (15 mL) was treated with lithium tri(tert-butoxy)aluminum hydride (1 mL, 1M in THF, 1 mmol) at -73° C. After stirring the mixture at -75° C. for 3 hr and then at -10° C. for 1.5 hr, the mixture was quenched with NaOH solution (1N, 2 mL). The solvents were removed and the residue was extracted with EtOAc. The organic layer was washed with water, and brine. After drying over anhyd. MgSO4 the solution was filtered and evaporated to yield the crude product. This crude product was then dissolved in a small amount of CH2Cl2 and poured on a column of silica gel. Elution with toluene:acetone mixture (9:1) gave 3α-hydroxy-17β-methoxy-5β-androstane (107 mg); mp 151-156° C.; TLC Rf (hexane:acetone 7:3)=0.18.

後処理

  1. waitat -10° C. for 1.5 hr
  2. customthe mixture was quenched with NaOH solution (1N, 2 mL)
  3. customThe solvents were removed
  4. extractionthe residue was extracted with EtOAc
  5. washThe organic layer was washed with water, and brine
  6. customAfter drying over anhyd
  7. filtrationMgSO4 the solution was filtered
  8. customevaporated
  9. customto yield the crude product
  10. additionpoured on a column of silica gel
  11. washElution with toluene

出典と根拠

ORDレコード
ord-adb2f65d0fca4899b2905dceda5fdde1
出典データセット
uspto-grants-1999_07
特許番号
US05925630

反応ノート

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